White light-emitting semiconductor devices

ABSTRACT

A white light-emitting semiconductor device having improved reproducibility of bright red. The device outputs light having a blue component, a green component, and a red component. Each of the light components (blue, green, and red) is based on a light-emitting semiconductor element and/or a phosphor that absorbs light emitted by a light-emitting semiconductor element and emits light through wavelength conversion. The outputted light has a spectrum which has a maximum wavelength in the range of 615-645 nm, and the intensity at a wavelength of 580 nm of the outputted light, which has been normalized with respect to luminous flux, is 80-100% of the intensity at a wavelength of 580 nm of standard light for color rendering evaluation, which has been normalized with respect to luminous flux.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.13/292,507 filed Nov. 9, 2011, which claims priority to PCT/JP10/064,306filed Aug. 24, 2010, which claims priority to Japanese PatentApplication Nos. 2009-195765 filed Aug. 26, 2009, 2010-020482 filed Feb.1, 2010, 2010-047173 filed Mar. 3, 2010, 2010-145095 filed Jun. 25,2010, and 2010-179063 filed Aug. 9, 2010, the entire contents of each ofwhich are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to white light-emitting devices whichoutput white light suitable for illumination. More particularly, theinvention relates to white light-emitting semiconductor devices whichare equipped with phosphors as light-emitting factors and with alight-emitting semiconductor element as an excitation source for thephosphors.

In the invention and in this description, light having a color which hasdeviations Duv from the black-body radiation locus in the range of −20to +20 is called white light. The definition of Duv (=1,000 duv) is inaccordance with JIS Z 8725:1999 “Method for Determining DistributionTemperature and Color Temperature or Correlated Color Temperature ofLight Sources”.

BACKGROUND ART

White LEDs which are a kind of white light-emitting semiconductor deviceconfigured so as to output white light on the basis of a combination ofa gallium nitride-based light-emitting diode (LED) element and aphosphor have recently come to be used also in illuminationapplications.

In illumination applications, there is a demand for white LEDs having acolor temperature of 3,500K or lower (patent document 1). Production ofwhite LEDs which have such a low color temperature and have a highluminance that renders the LEDs usable in illumination became possibledue to a success in the development of high-luminance red phosphors.Examples of the high-luminance red phosphors include red phosphors inwhich Eu²⁺ is used as an activator and crystals containing an alkalineearth siliconitride, alkaline earth silicate nitride, or alkaline earthsilicate are used as a base, such as CaAlSiN₃:Eu, which is disclosed inpatent document 2, (Sr, Ca)AlSiN₃:Eu, which is disclosed in patentdocument 3, Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, which is disclosedin patent document 4, and (Sr, Ba)₃SiO₅:Eu, which is disclosed in patentdocument 5. These red phosphors have a broad emission band having a fullwidth at half maximum exceeding 80 nm and, hence, white LEDs employingthese phosphors usually have a high color rendering index (CR1).

PRIOR-ART DOCUMENTS Patent Documents

-   Patent Document 1: JP-A-2004-103443-   Patent Document 2: JP-A-2006-8721-   Patent Document 3: JP-A-2008-7751-   Patent Document 4: JP-A-2007-231245-   Patent Document 5: JP-A-2008-50379

SUMMARY OF THE INVENTION Problem that the Invention is to Solve

However, white light-emitting semiconductor devices tend to be reducedin the reproducibility regarding bright red for which R9, which is oneof the special color rendering indexes, is used as an index. Thistendency is pronounced in white light-emitting semiconductor deviceshaving a low color temperature, such as LED lamps which emit white lighthaving a color temperature of 2,000-4,000K and are called warm whiteLEDs.

A major object of the invention is to provide a white light-emittingsemiconductor device having improved reproducibility regarding brightred.

Means for Solving the Problem

Essential points of the invention reside in the followings 1. to 6.

1. A white light-emitting semiconductor device which outputs lightcomprising a blue light component, a green light component, and a redlight component, wherein the blue light component includes light havingany wavelength in the range of 440-480 nm, the green light componentincludes light having any wavelength in the range of 515-560 nm, and thered light component includes light having any wavelength in the range of615-645 nm, and a source of the blue light component comprises alight-emitting semiconductor element and/or a first phosphor thatabsorbs the light emitted by a light-emitting semiconductor element andemits, through wavelength conversion, light including the blue lightcomponent, a source of the green light component comprises a secondphosphor that absorbs the light emitted by a light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the green light component, and a source of the red lightcomponent comprises a third phosphor that absorbs the light emitted by alight-emitting semiconductor element and emits, through wavelengthconversion, light including the red light component, the outputted lighthas a spectrum which has a maximum wavelength in the range of 615-645nm, and an intensity at a wavelength of 580 nm of the spectrum of theoutputted light which has been normalized with respect to luminous fluxis 80-100% of an intensity at a wavelength of 580 nm of the spectrum ofstandard light for color rendering evaluation which has been normalizedwith respect to luminous flux. In this white light-emittingsemiconductor device, the first phosphor preferably includes a bluephosphor, the second phosphor preferably includes a green phosphor, andthe third phosphor preferably includes a red phosphor. Furthermore, thesecond phosphor and/or the third phosphor may include a yellow phosphor.2. The white light-emitting semiconductor device according to 1. abovewherein the outputted light has a spectrum which has a maximumwavelength in the range of 615 or more and less than 630 nm, and anintensity at a wavelength of 580 nm of the spectrum of the outputtedlight which has been normalized with respect to luminous flux is85-100%, preferably 85-95%, of an intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux.3. The white light-emitting semiconductor device according to 1. above,wherein the outputted light has a spectrum which has a maximumwavelength in the range of 630-645 nm, and an intensity at a wavelengthof 580 nm of the spectrum of the outputted light which has beennormalized with respect to luminous flux is 90-100% of an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux.4. The white light-emitting semiconductor device according to any oneof 1. to 3. above, wherein the third phosphor comprises a first redphosphor and a second red phosphor, and the second red phosphor has alower relative intensity at a wavelength of 580 nm in an emissionspectrum, when the intensity at the peak wavelength is taken as 1, thanin the first red phosphor. In this white light-emitting semiconductordevice, the difference between the relative intensity at a wavelength of580 nm of the emission spectrum of the first red phosphor, with theintensity at the peak wavelength being taken as 1, and the relativeintensity at a wavelength of 580 nm of the emission spectrum of thesecond red phosphor, with the intensity at the peak wavelength beingtaken as 1, is preferably 0.2 or more, more preferably 0.3 or more.5. The white light-emitting semiconductor device according to 4. above,wherein a peak wavelength of the emission spectrum of the second redphosphor is present at a longer wavelength side than that of theemission spectrum of the first red phosphor.6. The white light-emitting semiconductor device according to 4. or 5.above, wherein at the first red phosphor includesSr_(x)Ca_(1−x)AlSiN₃:Eu (0<x<1),Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, or SrAlSi₄N₇:Eu. In this whitelight-emitting semiconductor device, it is preferred that a relativeintensity of the second red phosphor at a wavelength of 580 nm in anemission spectrum, with the intensity at the peak wavelength being takenas 1, is 0.05 or less. In this white light-emitting semiconductordevice, the second red phosphor preferably includes CaAlSiN₃:Eu.

Other essential points of the invention reside in the followings 7. to13.

7. A white light-emitting unit which emits white light containing a bluelight component, a green light component, and a red light component,wherein the blue light component includes light having any wavelength inthe range of 440-480 nm, the green light component includes light havingany wavelength in the range of 515-560 nm, and the red light componentincludes light having any wavelength in the range of 615-645 nm, and thewhite light-emitting unit comprises a light-emitting semiconductorelement, a first phosphor that absorbs the light emitted by thelight-emitting semiconductor element and emits, through wavelengthconversion, light including the blue light component, a second phosphorthat absorbs the light emitted by the light-emitting semiconductorelement and emits, through wavelength conversion, light including thegreen light component, and a third phosphor that absorbs the lightemitted by the light-emitting semiconductor element and emits, throughwavelength conversion, light including the red light component, thewhite light has a spectrum which has a maximum wavelength in the rangeof 615-645 nm, and an intensity at a wavelength of 580 nm of thespectrum of the white light which has been normalized with respect toluminous flux is 80-100% of an intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux.

In this white light-emitting unit, the first phosphor preferablyincludes a blue phosphor, the second phosphor preferably includes agreen phosphor, and the third phosphor preferably includes a redphosphor. Furthermore, the second phosphor and/or the third phosphor mayinclude a yellow phosphor.

8. A white light-emitting unit which emits white light containing a bluelight component, a green light component, and a red light component,wherein the blue light component includes light having any wavelength inthe range of 440-480 nm, the green light component includes light havingany wavelength in the range of 515-560 nm, and the red light componentincludes light having any wavelength in the range of 615-645 nm, and thewhite light-emitting unit comprises a light-emitting semiconductorelement that emits light including the blue light component, a secondphosphor that absorbs the light emitted by the light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the green light component, and a third phosphor that absorbsthe light emitted by the light-emitting semiconductor element and emits,through wavelength conversion, light including the red light component,the white light has a spectrum which has a maximum wavelength in therange of 615-645 nm, and an intensity at a wavelength of 580 nm of thespectrum of the white light which has been normalized with respect toluminous flux is 80-100% of the intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux. In this whitelight-emitting unit, the second phosphor preferably includes a greenphosphor, and the third phosphor preferably includes a red phosphor.Furthermore, the second phosphor and/or the third phosphor may include ayellow phosphor.9. The white light-emitting unit according to 7. or 8. above, whereinthe white light has a spectrum which has a maximum wavelength in therange of 615 nm or more and less than 630 nm, and an intensity at awavelength of 580 nm of the spectrum of the white light which has beennormalized with respect to luminous flux is 85-100%, preferably 85-95%,of an intensity at a wavelength of 580 nm of the spectrum of standardlight for color rendering evaluation which has been normalized withrespect to luminous flux.10. The white light-emitting unit according to 7. or 8. above, whereinthe white light has a spectrum which has a maximum wavelength in therange of 630-645 nm, and an intensity at a wavelength of 580 nm of thespectrum of the white light which has been normalized with respect toluminous flux is 90-100% of an intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux.11. The white light-emitting unit according to any of 7. to 10. above,wherein the third phosphor comprises a first red phosphor and a secondred phosphor, and the second red phosphor has a lower relative intensityat a wavelength of 580 nm in an emission spectrum, with the intensity atthe peak wavelength being taken as 1, than in the first red phosphor. Inthis white light-emitting unit, the difference between the relativeintensity at a wavelength of 580 nm of the emission spectrum of thefirst red phosphor, with the intensity at the peak wavelength beingtaken as 1, and the relative intensity at a wavelength of 580 nm of theemission spectrum of the second red phosphor, with the intensity at thepeak wavelength being taken as 1, is preferably 0.2 or more, morepreferably 0.3 or more.12. The white light-emitting unit according to 11. above, wherein a peakwavelength of the emission spectrum of the second red phosphor ispresent at a longer wavelength side than that of the emission spectrumof the first red phosphor.13. The white light-emitting unit according to 11. or 12. above, whereinthe first red phosphor includes Sr_(x)Ca_(1−x)AlSiN₃:Eu (0<x<1),Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, or SrAlSi₄N₇:Eu. In this whitelight-emitting unit, it is preferred that the relative intensity of thesecond red phosphor at a wavelength of 580 nm in an emission spectrum,with the intensity at the peak wavelength being taken as 1, is 0.05 orless. In this white light-emitting unit, the second red phosphorpreferably includes CaAlSiN₃:Eu.

Still other essential points of the invention reside in the followings14. to 16.

14. A white light-emitting semiconductor device comprising first to Nth(wherein N is an integer of 2 or larger) white light-emitting units eachequipped with a light-emitting semiconductor element and a wavelengthconversion part, in which the first to Nth white light-emitting unitseach emit primary white light and the primary white light emitted by theunits is mixed together, to form combined light as outputted light, andthe first to Nth white light-emitting units comprise a whitelight-emitting unit which emits first primary white light and a whitelight-emitting unit which emits second primary white light, and anintensity at a wavelength of 580 nm of the spectrum of the first primarywhite light which has been normalized with respect to luminous flux ishigher than an intensity at a wavelength of 580 nm of the spectrum ofstandard light for color rendering evaluation which has been normalizedwith respect to luminous flux, and an intensity at a wavelength of 580nm of the spectrum of the second primary white light which has beennormalized with respect to luminous flux is lower than an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux, and the outputted light has a spectrum which has a maximumwavelength in the range of 615-645 nm, and an intensity at a wavelengthof 580 nm of the spectrum of the outputted light which has beennormalized with respect to luminous flux is 80-100% of an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux.15. The white light-emitting semiconductor device according to 14.above, wherein the white light-emitting unit which emits first primarywhite light comprises a wavelength conversion part including a first redphosphor, and the white light-emitting unit which emits second primarywhite light comprises a wavelength conversion part including a secondred phosphor, and the second red phosphor has a lower relative intensityat a wavelength of 580 nm in an emission spectrum, when the intensity atthe peak wavelength is taken as 1, than in the first red phosphor.16. The white light-emitting semiconductor device according to 14. or15. above, wherein a difference in reciprocal correlated colortemperature between the first primary white light and the second primarywhite light is 50 MK⁻¹ or less, preferably 25 MK⁻¹ or less.

Effect of the Invention

According to the invention, a white light-emitting semiconductor devicehaving improved reproducibility regarding bright red is provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows emission spectra of white LEDs.

FIG. 2 shows an emission spectrum of a white LED and a spectrum ofstandard light for color rendering evaluation.

FIG. 3 shows an emission spectrum of a white LED and a spectrum ofstandard light for color rendering evaluation.

FIG. 4 shows an emission spectrum of a white LED.

FIG. 5 shows a combined spectrum and a spectrum of standard light forcolor rendering evaluation.

FIG. 6 shows an emission spectrum of a white LED and a spectrum ofstandard light for color rendering evaluation.

FIG. 7 shows an emission spectrum of a white LED and a spectrum ofstandard light for color rendering evaluation.

FIG. 8 shows an emission spectrum of a white LED.

FIG. 9 shows an emission spectrum of a white LED.

FIG. 10 shows an emission spectrum of a white LED.

FIG. 11 shows an emission spectrum of a white LED.

FIG. 12 shows an emission spectrum of a white LED.

FIG. 13 shows a relationship between 580-nm intensity ratio and R9.

FIG. 14 shows another relationship between 580-nm intensity ratio andR9.

FIG. 15 shows still another relationship between 580-nm intensity ratioand R9.

FIG. 16 shows an emission spectrum of a white LED.

FIG. 17 shows an emission spectrum of a white LED.

FIG. 18 shows an emission spectrum of a white LED.

FIG. 19 shows a chromaticity diagram (CIE 1931).

MODES FOR CARRYING OUT THE INVENTION

The white light-emitting semiconductor devices of the inventionpreferably include at least one white light-emitting unit. The whitelight-emitting unit includes a light-emitting semiconductor element anda phosphor which converts the wavelengths of the light emitted by thelight-emitting semiconductor element, and emits white light. There areno limitations on the configuration of optical coupling of thelight-emitting semiconductor element and the phosphor in the whitelight-emitting unit. The space between the two may be merely in thestate of being filled with a transparent medium (including air), or anoptical element such as, for example, a lens, optical fiber, lightguideplate, or reflecting mirror may have been interposed between the two.

A light-emitting semiconductor element which emits light having awavelength range of 360-490 nm can be advantageously used in the whitelight-emitting unit. The kind of the semiconductor which constitutes thelight-emitting part of the light-emitting semiconductor element and thestructure of the light-emitting part are not particularly limited.Preferred light-emitting semiconductor elements are light-emitting diodeelements having a pn junction type light-emitting part containing agallium nitride-based, zinc oxide-based, or silicon carbide-basedsemiconductor.

The state of the phosphor to be used in the white light-emitting unit isnot particularly limited, and the phosphor may be in a powder form ormay be a light-emitting ceramic containing a ceramic structure in whicha phosphor phase is contained. The powder-form phosphor is fixed by asuitable method before being used. The method for fixing is notparticularly limited. However, it is preferred to disperse particles ofthe phosphor in a transparent solid matrix made of a polymeric materialor glass or to deposit particles of the phosphor in a layeredarrangement on a surface of a suitable member by electrodeposition oranother technique.

A preferred white light-emitting unit is equipped with a bluelight-emitting diode element, a green phosphor, and a red phosphor, andemits white light which contains, as components thereof, part of theblue light emitted by the blue light-emitting diode element, green lightgenerated from other part of the blue light through wavelengthconversion by the green phosphor, and red light generated from stillother part of the blue light through wavelength conversion by the redphosphor. The blue light-emitting diode element usually has an emissionpeak wavelength of 440-470 nm. This white light-emitting unit may befurther equipped with a phosphor which absorbs part of the blue lightemitted by the blue light-emitting diode element and emits yellow light.

Another preferred white light-emitting unit is equipped with anultraviolet light-emitting diode element or purple light-emitting diodeelement, a blue phosphor, a green phosphor, and a red phosphor, andemits white light which contains, as components thereof, blue lightgenerated from part of the ultraviolet light or purple light emitted bythe light-emitting diode element through wavelength conversion by theblue phosphor, green light generated from other part of the ultravioletlight or purple light through wavelength conversion by the greenphosphor, and red light generated from still other part of theultraviolet light or purple light through conversion by the redphosphor. In the case of using a purple light-emitting diode element,part of the purple light emitted by the element may be contained as acomponent of the white light. In this white light-emitting unit, use ofa purple light-emitting diode element is preferred to use of anultraviolet light-emitting diode element because the former elementbrings about a reduction in Stokes shift loss.

The currently available purple light-emitting diode elements which arehighest in efficiency are InGaN-based purple light-emitting diodeelements. An InGaN-based light-emitting diode element is a pn junctiontype light-emitting diode element equipped with a doublehetero-structure in which an MQW active layer including an InGaN welllayer has been sandwiched between p type and n type GaN-based cladlayers, and it is known that this light-emitting diode element has amaximum luminescent efficiency when regulated so as to have an emissionpeak wavelength in the range of 410-430 nm (G. Chen, et al., Phys. Stat.Sol. (a) 205, No. 5, 1086-1092 (2008)). Meanwhile, in high-efficiencyblue phosphors, the excitation efficiency is generally high in theultraviolet to near-ultraviolet regions and abruptly decreases withincreasing wavelength on the longer-wavelength side of a wavelength of405 nm. When such excitation characteristics of the blue phosphors istaken into account, the purple light-emitting diode element mostsuitable for a white light-emitting unit is an InGaN-basedlight-emitting diode element which has an emission peak wavelength inthe range of 400-420 nm, in particular, in the range of 405-415 nm.

There are no particular limitations on the configuration of the whitelight-emitting unit, and reference can be made at will to theconfigurations of known white light-emitting devices based on acombination of a light-emitting semiconductor element and a phosphor. Apreferred example includes the structure of a general white LED. Namely,the white light-emitting unit can be made to have a structure obtainedby mounting one or more light-emitting diode elements in a package,e.g., a shell type package or an SMD type package, and encapsulating thepackage with a light-transmitting encapsulating material to which aphosphor has been added.

In a white light-emitting unit according to another preferred example, alight-emitting diode element is directly mounted on a circuit boardwithout using a package. This white light-emitting unit includes aso-called chip-on-board type unit. A phosphor is disposed by a suitablemethod in a position which is irradiated with the light emitted by thelight-emitting diode element. For example, a light-transmitting siliconeresin composition containing a phosphor powder dispersed therein isapplied to the surface of the light-emitting diode element.Alternatively, a phosphor powder is deposited on the surface of thelight-emitting diode element by a technique such as electrodeposition.In still another method, a light-transmitting sheet which contains aphosphor and which has been prepared in a separate step is disposed overthe light-emitting diode element. This sheet may be a sheet containing alight-emitting ceramic which contains a phosphor phase, or may be a filmmade of a light-transmitting resin composition in which a phosphorpowder has been dispersed. This film may be a film superposed on asurface of a transparent plate made of a resin, glass, etc.

The white light-emitting semiconductor devices of the invention may be adevice which is equipped with a plurality of white light-emitting unitsand by which combined light obtained by mixing the primary white lightemitted by the individual white light-emitting units is outputted. Inthis embodiment, the plurality of white light-emitting units can includetwo white light-emitting units which differ from each other in emissionspectrum.

It is not essential that the white light-emitting semiconductor devicesof the invention should be equipped with a white light-emitting unit. Apossible example is equipped with a blue light-emitting unit, a greenlight-emitting unit, and a red light-emitting unit and outputs whitelight which contains, as components thereof, blue light emitted by theblue light-emitting unit, green light emitted by the greenlight-emitting unit, and red light emitted by the red light-emittingunit. The blue light-emitting unit is a light-emitting unit which isequipped with an ultraviolet light-emitting diode element or purplelight-emitting diode element and a blue phosphor and which has beenconfigured so that the ultraviolet light or purple light emitted by thelight-emitting diode element undergoes wavelength conversion by theaction of the blue phosphor and the resultant blue light is emitted. Thegreen light-emitting unit is a light-emitting unit which is equippedwith an ultraviolet light-emitting diode element or purplelight-emitting diode element and a green phosphor and which has beenconfigured so that the ultraviolet light or purple light emitted by thelight-emitting diode element undergoes wavelength conversion by theaction of the green phosphor and the resultant green light is emitted.The red light-emitting unit is a light-emitting unit which is equippedwith an ultraviolet light-emitting diode element or purplelight-emitting diode element and a red phosphor and which has beenconfigured so that the ultraviolet light or purple light emitted by thelight-emitting diode element undergoes wavelength conversion by theaction of the red phosphor and the resultant red light is emitted.

The white light-emitting semiconductor devices of the invention may be adevice which is equipped with various kinds of light-emitting units,such as the blue light-emitting unit, green light-emitting unit, and redlight-emitting unit described above, besides a white light-emitting unitand by which combined light obtained by mixing the light emitted by theindividual light-emitting units is outputted.

The white light-emitting semiconductor devices of the invention outputlight which contains a blue light component, a green light component,and a red light component regardless of whether the devices are equippedwith a white light-emitting unit or not. The blue light component atleast includes light having any wavelength in the range of 440-480 nm,the green light component at least includes light having any wavelengthin the range of 515-560 nm, and the red light component at leastincludes light having any wavelength in the range of 615-645 nm. Thesource of the blue light component includes a light-emittingsemiconductor element and/or a phosphor which absorbs the light emittedby the light-emitting semiconductor element and emits, throughwavelength conversion, light including the blue light component. On theother hand, the source of the green light component essentially includesa phosphor which absorbs the light emitted by a light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the green light component. Furthermore, the source of the redlight component essentially includes a phosphor which absorbs the lightemitted by a light-emitting semiconductor element and emits, throughwavelength conversion, light including the red light component. To usephosphors, which have a broader emission band than light-emittingsemiconductor elements, as sources of the green light component and redlight component is an exceedingly important factor in obtaining a whitelight-emitting device having satisfactory color rendering properties.

In the white light-emitting semiconductor devices of the invention, asuitable light-emitting semiconductor element which is usable as asource of the blue light component is an InGaN-based blue light-emittingdiode element. A preferred example may be equipped with a firstlight-emitting diode element having an emission peak wavelength in therange of 440-470 nm and a second light-emitting diode element having anemission peak wavelength in the range of 470-500 nm, from the standpointof enhancing color rendering properties. In this configuration, theemission peak wavelength of the first light-emitting diode element andthe emission peak wavelength of the second light-emitting diode elementare separated from each other by 10 nm or more, preferably by 20 nm ormore. As the InGaN-based light-emitting diode element having an emissionpeak wavelength in the range of 470-500 nm, use can advantageously bemade of a light-emitting diode element produced by depositing aGaN-based semiconductor including a light-emitting InGaN layer on anonpolar or semipolar GaN substrate by epitaxial growth.

In the white light-emitting semiconductor devices of the invention, ablue phosphor capable of being excited by ultraviolet to purple lightcan be advantageously used as a source for emitting the blue lightcomponent through wavelength conversion. The term “blue phosphor” meansa phosphor which emits light having a color that is classified as“PURPULISH BLUE”, “BLUE”, or “GREENISH BLUE” in the xy chromaticitydiagram (CIE 1931) shown in FIG. 19. The kind of this blue phosphor isnot particularly limited. However, suitable examples thereof includeblue phosphors each composed of Eu²⁺ as an activator and crystalscontaining an alkaline earth aluminate or alkaline earth halophosphateas a base, such as, for example, (Ba, Sr, Ca)MgAl₁₀O₁₇:Eu and (Ca, Sr,Ba)₅(PO₄)₃Cl:Eu. Preferred of these are BaMgAl₁₀O₁₇:Eu andSr_(5-y)Ba_(y)(PO₄)₃Cl:Eu (0<y<5), which have high emission efficiencyand a broad emission band. For enhancing the color rendering propertiesof the white light-emitting semiconductor device, it is effective to usea blue phosphor having a broad emission band.

In the white light-emitting semiconductor devices of the invention, agreen phosphor can be advantageously used as a source of the green lightcomponent. The term “green phosphor” means a phosphor which emits lighthaving a color that is classified as “GREEN” or “YELLOWISH GREEN” in thexy chromaticity diagram (CIE 1931) shown in FIG. 19. The kind of thisgreen phosphor is not particularly limited. For example, known greenphosphors including Eu²⁺, Ce³⁺, or the like as an activator can beadvantageously used. Suitable green phosphors employing Eu²⁺ as anactivator are green phosphors including crystals containing an alkalineearth silicate, alkaline earth silicate nitride, or Sialon as a base.This kind of green phosphor can usually be excited using an ultravioletto blue light-emitting semiconductor element. Examples of the greenphosphors employing crystals of an alkaline earth silicate as a baseinclude (Ba, Ca, Sr, Mg)₂SiO₄:Eu and (Ba, Sr, Ca)₂(Mg, Zn)Si₂O₇:Eu.Examples of the green phosphors employing crystals of an alkaline earthsilicate nitride as a base include (Ba, Ca, Sr)₃Si₆O₁₂N₂:Eu, (Ba, Ca,Sr)₃Si₆O₉N₄:Eu, and (Ca, Sr, Ba)Si₂O₂N₂:Eu.

Examples of the green phosphors employing Sialon crystals as a baseinclude β-Sialon:Eu, Sr₃Si₁₃Al₃O₂N₂₁:Eu, and Sr₅Al₅Si₂₁O₂N₃₅:Eu. TheSr₃Si₁₃Al₃O₂N₂₁:Eu is disclosed in International Publication No.2007-105631, pamphlet, and the Sr₅Al₅Si₂₁O₂N₃₅:Eu is disclosed inInternational Publication No. 2009-072043, pamphlet. Suitable greenphosphors employing Ce³⁺ as an activator include green phosphorsincluding crystals of a garnet-type oxide as a base, such as, forexample, Ca₃(Sc, Mg)₂Si₃O₁₂:Ce, and green phosphors including crystalsof an alkaline earth metal scandate as a base, such as, for example,CaSc₂O₄:Ce. This kind of green phosphor is suitable for use in the casewhere a blue light-emitting semiconductor element is used as anexcitation source.

The green phosphors shown above as suitable examples have satisfactorydurability as compared with sulfide-based green phosphors such asZnS:Cu,Al. In particular, the green phosphors in which the base crystalsare an alkaline earth silicate nitride or Sialon have an advantage thatthe covalent nature of interatomic bonds in the base crystals is highbecause nitrogen is contained and, hence, these phosphors show highlyexcellent durability and heat resistance. Meanwhile, use of a phosphorincluding crystals of a sulfur-containing compound as a base is notrecommended regardless of whether the phosphor is a green phosphor ornot. This is because there are cases where the sulfur which is liberatedeven in a slight amount from the base crystals reacts with metalscontained in the light-emitting semiconductor element, package,encapsulating material, etc., resulting in generation of a blacksubstance.

In the light-emitting semiconductor devices of the invention, a redphosphor, in particular, a red phosphor which has an emission bandhaving a full width at half maximum of 80 nm or more, can beadvantageously used as a source of the red light component. Redphosphors of all kinds which have such emission characteristics can beused. However, suitable examples thereof include red phosphors eachcomposed of Eu²⁺ as an activator and crystals containing an alkalineearth siliconitride, alkaline earth silicate nitride, α-Sialon, oralkaline earth silicate as a base. This kind of red phosphor can usuallybe excited using an ultraviolet to blue light-emitting semiconductorelement. Examples of the red phosphors employing crystals of an alkalineearth siliconitride as a base include (Ca, Sr, Ba)AlSiN₃:Eu, (Ca, Sr,Ba)₂Si₅N₈:Eu, and SrAlSi₄N₇:Eu. The SrAlSi₄N₇:Eu is a red phosphordisclosed in, for example, JP-A-2008-150549. Examples of the redphosphors employing crystals of an alkaline earth silicate nitride as abase include (CaAlSiN₃)_(1−x)(Si_((3n+2)/4)N_(n)O)_(x):Eu. Examples ofthe red phosphors employing crystals of an alkaline earth silicate as abase include (Sr, Ba)₃SiO₅:Eu. As in the case of the green phosphors,the red phosphors in which the base crystals contain nitrogen havehighly excellent durability and heat resistance. Of these, (Ca, Sr,Ba)AlSiN₃:Eu and (CaAlSiN₃)_(1−x)(Si_((3n+2)/4)N_(n)O)_(x):Eu can beespecially advantageously used because these two kinds of red phosphorshave a high luminescent efficiency.

The term “red phosphor” in the invention means a phosphor which emitslight having a color that is classified as “RED”, “REDDISH ORANGE”, or“ORANGE” in the xy chromaticity diagram (CIE 1931) shown in FIG. 19.Most of such phosphors have an emission peak wavelength in the range of590-700 nm.

In the white light-emitting semiconductor devices of the invention, ayellow phosphor can be used as part of sources of the green lightcomponent or red light component. The term “yellow phosphor” means aphosphor which emits light having a color that is classified as “YELLOWGREEN”, “GREENISH YELLOW”, “YELLOW”, or “YELLOWISH ORANGE” in the xychromaticity diagram (CIE 1931) shown in FIG. 19. Preferred yellowphosphors include phosphors each composed of Ce³⁺ as an activator andcrystals of a garnet-type oxide as a base, such as, for example, (Y,Gd)₃Al₅O₁₂:Ce and Tb₃Al₅O₁₂:Ce. Other preferred yellow phosphors includephosphors each composed of Ce³⁺ as an activator and crystals of alanthanum siliconitride as a base, such as, for example, La₃Si₆N₁₁:Ceand Ca_(1.5x)La_(3−x)Si₆N₁₁:Ce. Although suitable for use in the casewhere a blue light-emitting semiconductor element is used as anexcitation source, this kind of yellow phosphor can be excited also withthe light emitted by a blue phosphor.

The white light-emitting semiconductor devices of the invention areintended to emit light suitable for white illumination, that is, lightwhich has a color having deviations Duv from the black-body radiationlocus in the range of −20 to +20, preferably in the range of −6.0 to+6.0. It is a matter of course that the color of outputted light can beset by regulating an intensity balance among the light componentsconstituting the outputted light. In an embodiment equipped with a whitelight-emitting unit, techniques employed in known white light-emittingdevices (e.g., white LEDs) based on a combination of a light-emittingsemiconductor element and a phosphor can be suitably used to set thecorrelated color temperature of the white light emitted by the whitelight-emitting unit.

The present inventors found that a white light-emitting semiconductordevice having satisfactory reproducibility of bright red is obtainedwhen the following two requirements are satisfied. The first requirementis that the light outputted by the light-emitting device should have amaximum wavelength in the range of 615-645 nm. The second requirement isthat an intensity at a wavelength of 580 nm of the spectrum of the lightoutputted by the light-emitting device which has been normalized withrespect to luminous flux should have, should be 80-100% of the intensityat a wavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux.

It is surprising that even when the maximum wavelength which ispossessed by the spectrum of the outputted light in the red spectralregion (590-780 nm) is shorter than 630 nm, the special color renderingindex R9 of the white light-emitting semiconductor device is improved toa considerable degree by making the light-emitting device satisfy thesecond requirement. This fact indicates that the Stokes shift loss of alight-emitting device can be reduced without sacrificing reproducibilityof bright red.

Meanwhile, there are cases where a white light-emitting semiconductordevice which outputs light having a spectrum that contains a deep-redcomponent in a large amount but which does not satisfy the secondrequirement has an exceedingly low value of special color renderingindex R9. The inventors ascertained this phenomenon through experimentalproduction of a white LED employing red phosphor CaAlSiN₃:Eu having anemission peak wavelength of about 660 nm. It seems that this fact hasconventionally been unknown even to persons skilled in the art and is anew finding.

In the following explanations, the proportion of the intensity (I1) atwavelength 580 nm of the spectrum of light outputted by a light-emittingdevice which has been normalized with respect to luminous flux to theintensity (I2) at wavelength 580 nm of the spectrum of standard lightfor color rendering evaluation which has been normalized with respect toluminous flux (I1/I2) is often called “580-nm intensity ratio”.

With respect to the second requirement, a preferred 580-nm intensityratio varies depending on the wavelength range where a maximumwavelength according to the first requirement is present. When thespectrum of outputted light has a maximum wavelength in the range of 615nm to 630 nm, excluding 630 nm, then the 580-nm intensity ratio ispreferably 85-100%, more preferably 85-95%. On the other hand, when thespectrum of outputted light has a maximum wavelength in the range of630-645 nm, then the 580-nm intensity ratio is preferably 90-100%.

The term “standard light for color rendering evaluation” used in thesecond requirement means standard light as provided for in JapanIndustrial Standards JIS Z8726:1990, which prescribes for a method forevaluating the color rendering properties of light sources. When a whitelight-emitting semiconductor device as a sample light source has acorrelated color temperature lower than 5,000K, then the standard lightis light from a full radiator. When a white light-emitting semiconductordevice has a correlated color temperature of 5,000K or higher, thestandard light is CIE daylight. The definition of full radiator and CIEdaylight is in accordance with JIS Z8720:2000 (correspondinginternational standard, ISO/CIE 10526:1991).

The term “spectrum of light which has been normalized with respect toluminous flux” used in the second requirement means a spectrum (spectralradiant flux Φ_(e) in the following mathematical expression (1)) whichhas been normalized so that the luminous flux Φ determined by thefollowing mathematical expression (1) is 1 (unity).[Math. 1]Φ=K _(m)∫₃₈₀ ⁷⁸⁰ V _(λ)Φ_(e) dλ  (1)

In mathematical expression (1),

Φ is luminous flux [lm],

K_(m) is maximum spectral luminous efficiency [lm/W],

V_(λ) is spectral luminous efficiency function for photopic vision,

Φ_(e) is spectral radiant flux [W/nm], and

λ is wavelength [nm].

For obtaining a white light-emitting semiconductor device whichsatisfies the first requirement, a red phosphor which has an emissionband having a full width at half maximum of 80 nm or more and has anemission peak wavelength of 625 nm or longer may be used as a source ofthe red light component. In the case where only one red phosphor is tobe used, it is preferred to employ a red phosphor which has an emissionpeak wavelength in the range of 625-655 nm. In the case where aplurality of red phosphors are to be used, it is possible to select atleast one from red phosphors having an emission peak wavelength shorterthan λ₁ and to select another at least one from red phosphors having anemission peak wavelength not shorter than λ₁. Symbol λ₁ represents anywavelength in the range of 625-655 nm. All of the plurality of redphosphors can be selected from red phosphors having an emission peakwavelength in the range of 625-655 nm. In one example, all of theplurality of red phosphors may be selected from red phosphors having anemission peak wavelength of 630 m or longer.

It is desirable that a phosphor for use as a source of the green lightcomponent and a phosphor for use as a source of the red light componentshould be suitably selected in order that the second requirement besatisfied. For example, when one or more green phosphors and one or morered phosphors are used as the former and latter sources, respectively,and when all these phosphors each have an emission spectrum in which therelative intensity at a wavelength of 580 nm (the relative intensity atwavelength 580 nm of the emission spectrum of each phosphor, with theintensity at the peak wavelength being taken as 1; this relativeintensity is hereinafter referred to also as “580-nm relativeintensity”) is less than 0.3, then there is a high possibility that thelight-emitting device might have a 580-nm intensity ratio lower than80%. Conversely, when both the green phosphors and the red phosphorsused each have a 580-nm relative intensity higher than 0.5, then thereis a high possibility that the light-emitting device might have a 580-nmintensity ratio exceeding 100%.

A suitable and simple method is to use, in combination, a plurality ofred phosphors differing in 580-nm relative intensity. The secondrequirement can be thereby satisfied. For example, it is assumed thatuse of a red phosphor (red phosphor 1) as the only red phosphor resultsin a white light-emitting semiconductor device which has a satisfactoryvalue of color rendering index Ra (e.g., 85) but which has a low valueof special color rendering index R9 (e.g., below 60). This whitelight-emitting semiconductor device is examined for 580-nm intensityratio. If the 580-nm intensity ratio thereof is greater than 100%, this580-nm intensity ratio can be reduced to 100% or less by using, inaddition to the red phosphor 1, a red phosphor (red phosphor 2) whichhas a lower 580-nm relative intensity than the red phosphor 1.Conversely, if the 580-nm intensity ratio of the white light-emittingsemiconductor device obtained using the red phosphor 1 as the only redphosphor is less than 80%, a red phosphor (red phosphor 3) having ahigher 580-nm relative intensity than the red phosphor 1 may beadditionally used besides the red phosphor 1. The larger the differencein 580-nm relative intensity between the red phosphor 1 and each of thered phosphor 2 and the red phosphor 3, the larger the change in 580-nmintensity ratio which the white light-emitting device undergoes as aresult of additional use of a small amount of the red phosphor 2 or redphosphor 3. Consequently, the difference in 580-nm relative intensity ispreferably 0.2 or more, more preferably 0.3 or more.

In the example shown above, in the case where the red phosphor 2 isadditionally used, it is preferred that the red phosphor 2 should have alonger emission peak wavelength than the red phosphor 1. Additional useof such red phosphor 2 not only reduces the 580-nm intensity ratio ofthe white light-emitting device but also increases the maximumwavelength possessed in the red spectral region (590-780 nm) by thespectrum of the light outputted by the light-emitting device. There is atendency that the longer the maximum wavelength, the higher the 580-nmintensity ratio which brings about a maximum value of R9. Consequently,this red phosphor 2 imparts a high R9-improving effect when additionallyused even in a small amount. Namely, reproducibility regarding brightred can be improved while minimizing various influences caused byadditional use of the red phosphor 2.

Even when used alone, Sr_(x)Ca_(1−x)AlSiN₃:Eu (0<x<1) andCa_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, among red phosphors, give awhite light-emitting semiconductor device having satisfactory values ofcolor rendering index Ra and special color rendering index R9. However,by using either of the two red phosphors in combination with a redphosphor which has a longer emission peak wavelength and has a lower580-nm relative intensity (e.g., CaAlSiN₃:Eu), a white light-emittingdevice having a further improved value of special color rendering indexR9 can be obtained. Red phosphor SrAlSi₄N₇:Eu, which is akin in emissionspectrum to Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, is expected toproduce the same effect.

In order that the second requirement be satisfied, a combination of aplurality of green phosphors differing in 580-nm relative intensity or acombination of a plurality of yellow phosphors differing in 580-nmrelative intensity can be used in place of using a plurality of redphosphors differing in 580-nm relative intensity in combination.

An embodiment of the white light-emitting semiconductor devices of theinvention may be a light-emitting device which has first to Nth (whereinN is an integer of 2 or larger) white light-emitting units each equippedwith a light-emitting semiconductor element and a wavelength conversionpart, and in which the first to Nth white light-emitting units each emitprimary white light and the primary white light emitted by the units ismixed together, the resultant combined light being emitted as outputtedlight. This light-emitting device may be one which includes a whitelight-emitting unit that emits first primary white light (whitelight-emitting unit 1) and a white light-emitting unit that emits secondprimary white light (white light-emitting unit 2), and in which anintensity at a wavelength of 580 nm of the spectrum of the first primarywhite light which has been normalized with respect to luminous flux ishigher than an intensity at a wavelength of 580 nm of the spectrum ofstandard light for color rendering evaluation which has been normalizedwith respect to luminous flux, and an intensity at a wavelength of 580nm of the spectrum of the second primary white light which has beennormalized with respect to luminous flux is lower than an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux. In this case, the electric power to be applied to the whitelight-emitting unit 1 and the electric power to be applied to the whitelight-emitting unit 2 are controlled to regulate the proportion of thefirst primary white light and the proportion of the second primary whitelight in the light outputted by the light-emitting device. Thus, a statein which the light-emitting device satisfies the second requirement canbe attained.

In order that such control of the R9 of a white light-emitting device,which is based on control of the proportions of the electric power to beapplied to two white light-emitting units, might be rendered possible, ared phosphor and another red phosphor which differ from each other in580-nm relative intensity can be used for the white light-emitting unit1 and the white light-emitting unit 2, respectively. In this embodiment,by reducing the difference in reciprocal correlated color temperaturebetween the first primary white light and the second primary whitelight, the light outputted by the white light-emitting semiconductordevice can be inhibited from changing in color when the emissionintensity ratio between the white light-emitting unit 1 and the whitelight-emitting unit 2 is changed. For this purpose, the difference inreciprocal correlated color temperature between the first primary whitelight and the second primary white light is regulated to preferably 50MK⁻¹ or less, more preferably 25 MK⁻¹ or less.

The simulated white light-emitting devices S-1 shown in Table 6, whichwill be given later, can be regarded as a simulation example of whitelight-emitting semiconductor devices according to this embodiment. Inthe simulated white light-emitting devices S-1, white LED samples V-2and V-7 correspond to the white light-emitting unit 1 and whitelight-emitting unit 2. When the intensity ratio between the primarywhite light emitted by V-2 and the primary white light emitted by V-7changed from 10:0 to 0:10, then the color rendering properties of thesimulated white light-emitting devices S-1 changed considerably.However, since these two kinds of primary white color had an exceedinglysmall chromaticity difference, the light outputted by the simulatedwhite light-emitting devices S-1 showed substantially no change inchromaticity.

Other techniques for making the second requirement be satisfied includefiltering of outputted light. This technique can be employed when it isnecessary that the 580-nm intensity ratio of the outputted light shouldbe lowered in order that the second requirement be satisfied. In thistechnique, light having a wavelength band including 580 nm is partlyremoved from the light outputted by a white light-emitting semiconductordevice, by filtering with a means for filtration. The specificconfiguration of the filtration means is not limited, and the filtrationmeans can be any desired light-transmitting member or light-reflectingmember which has the function of partly removing light having awavelength band including 580 nm from transmitted light or reflectedlight on the basis of an optical principle or absorption by alight-absorbing substance. Preferred examples of the filtration meanswhich is a light-transmitting member include the minus filter (opticalfilter) disclosed in JP-A-2010-39206 and the absorption filter disclosedin JP-A-2009-251511, which contains as a light-absorbing substance awavelength-selective absorption dye containing a cyanine compound,squarylium compound, tetraazaporphyrin compound, or the like. Examplesof the filtration means which is a light-reflecting member include alight reflector in which such a wavelength-selective absorption dye hasbeen fixed to the reflection surface and a light reflector which has areflection surface formed from a resin containing such awavelength-selective absorption dye.

The position in which the filtration means is to be disposed is notlimited. For example, in the case of a white light-emittingsemiconductor device including a white light-emitting unit, thefiltration means can be disposed within the white light-emitting unit toconfigure the device so that light having a wavelength band including580 nm is removed by the filtration means beforehand and the residualwhite light is emitted from the unit. For this purpose, the filtrationmeans (light-transmitting member or light-reflecting member) may bedisposed on the path along which the light having a wavelength bandincluding 580 nm generated in the white light-emitting unit passesbefore being emitted from the unit. In one embodiment, thewavelength-selective absorption dye can be added to a transparent solidmatrix (wavelength conversion part) disposed in the white light-emittingunit and containing phosphor particles dispersed therein. Namely, thisembodiment has a configuration in which the filtration means has beenintegrated with the wavelength conversion part.

In the case of a white light-emitting semiconductor device equipped withan optical system by which the white light emitted by the whitelight-emitting unit is guided to the outside, the filtration means forremoving part of light having a wavelength band including 580 nm fromthe white light can be incorporated into part of the optical system. Inthis case, the filtration means of a detachable or replaceable type canbe incorporated into the optical system so that the amount of light tobe removed by filtering can be regulated. According to thisconfiguration, the filtration means can be made to function inaccordance with the spectrum of white light emitted from the whitelight-emitting unit and the 580-nm intensity ratio of the light-emittingdevice can be optimized thereby. Namely, the special color renderingindex R9 of the light-emitting device can be maximized.

In the case of a white light-emitting semiconductor device which isequipped with a plurality of light-emitting units and by which combinedlight obtained by mixing the multiple kinds of light respectivelyemitted by the plurality of light-emitting units is outputted, lighthaving a wavelength band including 580 nm may be removed using a generalshort-pass filter or long-pas filter from the light emitted by at leastone light-emitting unit. Thus, the 580-nm intensity ratio can belowered. Illustratively stated, in the case of a white light-emittingsemiconductor device equipped with a blue light-emitting unit, greenlight-emitting unit, and red light-emitting unit, a short-pass filter isused to remove a longer-wavelength-side wavelength component havingwavelengths including 580 nm from the light emitted by the greenlight-emitting unit. Alternatively, a long-pass filter is used to removea shorter-wavelength-side wavelength component having wavelengthsincluding 580 nm from the light emitted by the red light-emitting unit.Thus, the 580-nm intensity ratio can be reduced.

The white light-emitting semiconductor devices of the invention shouldnot be construed as being limited to light-emitting devices capable ofoutputting white light only, and may further have the function ofgenerating light other than white light. The white light-emittingsemiconductor devices of the invention may be white light-emittingdevices capable of being changed in color temperature, that is, whitelight-emitting devices which are capable of outputting white lighthaving various color temperatures. Furthermore, the white light-emittingsemiconductor devices of the invention may be white light-emittingdevices in which the color rendering properties can be changed orregulated by lighting mode switching.

<Experimental Results>

The results of experiments (including simulations) made by the presentinventors are described below. The finding that the reproducibilityregarding bright red of a white light-emitting semiconductor device isimproved when the first requirement and second requirement describedabove are satisfied was obtained through the experiments. Table 1 is alist of the phosphors used in the experiments.

TABLE 1 Properties of emission spectrum Emission peak wavelength Full[nm] width (excitation at half Relative wavelength maximum intensityName Classification General formula [nm]) [nm] at 580 nm BAM blueBaMgAl₁₀O₁₇:Eu 455 (400) 52 — fluorescent substance SCA blueSr₅(PO₄)₃Cl:Eu 450 (405) 28 — fluorescent substance SBCA blueSr_(5−y)Ba_(y)(PO₄)₃Cl:Eu 453 (410) 62 — fluorescent substance BSS green(Ba,Ca,Sr,Mg)₂SiO₄:Eu 529 (405) 66 0.32 fluorescent 529 (450) 67 0.33substance BSON green (Ba,Ca,Sr)₃Si₆O₁₂N₂:Eu 535 (405) 71 0.45fluorescent substance β-SiAlON green Si_(6−z)Al_(z)N_(8−z)O_(z):Eu 542(400) 56 0.41 fluorescent substance CSMS green Ca₃(Sc,Mg)₂Si₃O₁₂:Ce 516(455) 107 0.69 fluorescent substance CSO green CaSc₂O₄:Ce 520 (455) 1010.65 fluorescent substance YAG yellow Y₃Al₅O₁₂:Ce 559 (465) 113 0.93fluorescent substance SBS red (Sr,Ba)₃SiO₅:Eu 596 (455) 80 0.88fluorescent 592 (402) 84 0.92 substance SCASN redSr_(x)Ca_(1−x)AlSiN₃:Eu 626 (405) 88 0.35 fluorescent 628 (450) 87 0.31substance CASON-1 red Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu 643 (405)116 0.46 fluorescent 643 (450) 106 0.35 substance CASON-2 redCa_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu 638 (400) 127 0.57 fluorescent641 (450) 111 0.43 substance CASN-1 red CaAlSiN₃:Eu 659 (400) 90 0.05fluorescent substance CASN-2 red CaAlSiN₃:Eu 648 (455) 88 0.13fluorescent substance

Table 1 shows the name used in the description, classification by thecolor of emitted light, general formula, and properties of emissionspectrum, with respect to each phosphor. The properties of emissionspectrum shown are the peak wavelength (emission peak wavelength) andfull width at half maximum of the main emission band and “relativeintensity at 580 nm”. The values of these properties each was determinedthrough a measurement which was made when the phosphor was excited atthe wavelength shown in the parentheses in the column Emission peakwavelength. The “relative intensity at 580 nm” has the same meaning asthe 580-nm relative intensity described above, and is the value of theintensity at wavelength 580 nm of the emission spectrum relative to theintensity at the emission peak wavelength (emission peak intensity) ofthe emission spectrum, which is taken as 1.

Emission spectra of the phosphors were examined by an ordinary method inuse in this field, except for the properties of the emission spectrum ofSBS which was obtained at an excitation wavelength of 402 nm. Theseproperties are based on the results of an examination of an emissionspectrum of a red light-emitting unit. This red light-emitting unit wasproduced by mounting one InGaN-based light-emitting diode chip having anemission peak wavelength of 402 nm in a 3528 SMD type PPA resin packageand encapsulating the package with a silicone resin composition to whichpowdery SBS had been added. The light-emitting diode chip had a size of350 μm square, and the current which was applied to the redlight-emitting unit during emission spectrum examination was 20 mA.

CASON-1 and CASON-2, which each are a red phosphor represented by thegeneral formula Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, differ inemission characteristics probably because of a difference in the valueof x, etc. The base of Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu is asolid solution between CaAlSiN₃ and Si₂N₂O, and is sometimes expressedby (CaAlSiN₃)_(1−x)(Si₂N₂O)_(x). There are cases where these phosphorsare often represented by the general formula CaAISi(N, O)₃:Eu.

CASN-1 and CASN-2, which each are a red phosphor represented by thegeneral formula CaAlSiN₃:Eu, differ in emission characteristics. Thefact that phosphors represented by the same general formula (phosphorswhich are equal in the basic structure of the base) show differentemission characteristics by the influence of a factor, such as, forexample, activator concentration, impurity concentration, or differenceof base composition from the general formula, and that phosphors havingvarious emission characteristics according to requests from the marketare being produced while utilizing that fact are well known in thistechnical field.

Lists of white LED samples produced using the phosphors given in Table 1are shown in Table 2 and Table 3. In the eleven kinds of samples rangingfrom V-1 to V-11 shown in Table 2, a purple light-emitting diode elementhaving an emission peak wavelength of about 405 nm is used as anexcitation source for the phosphors. On the other hand, in the ten kindsof samples ranging from B-1 to B-10 shown in Table 3, a bluelight-emitting diode element having an emission peak wavelength of about450 nm is used as a source of blue light and as an excitation source forthe phosphors.

TABLE 2 Sample LED Name of phosphor Proportions of phosphors [wt %] nameelement Blue Green Red Blue Green Red V-1 purple BAM BSS CASON-1 9.0 1.24.3 V-2 purple BAM BSS CASON-2 8.8 1.2 4.6 V-3 purple BAM BSS CASON-2,9.0 1.2 4.0 (CASON-2), CASN-1 0.2 (CASN-1) V-4 purple BAM BSS CASON-2,9.0 1.4 3.8 (CASON-2), CASN-1 0.4 (CASN-1) V-5 purple BAM BSS SBS 8.20.8 7.0 V-6 purple BAM BSS SCASN 15.4 2.0 1.7 V-7 purple BAM BSS CASN-112.1 2.6 1.4 V-8 purple SCA BSS CASON-1 6.6 2.6 5.4 V-9 purple SCA BSSCASON-2 6.6 2.4 5.6 V-10 purple SBCA β-SiAlON CASON-1 3.5 2.2 4.8 V-11purple SBCA BSON CASON-1 3.5 1.7 4.7

TABLE 3 Sam- Proportions of ple LED Kind of phosphor phosphors [wt %]name element Green Yellow Red Green Yellow Red B-1 blue BSS — CASON-16.5 — 6.8 B-2 blue BSS — CASON-2 6.5 — 8.0 B-3 blue CSMS — SCASN 7.9 —2.1 B-4 blue CSO — SCASN 7.9 — 2.1 B-5 blue — YAG CASN-2 — 8.4 3.3 B-6blue CSMS — CASN-2 10.4  — 4.1 B-7 blue CSMS YAG CASN-2 5.2 4.2 3.7 B-8blue CSMS YAG CASN-2 9.3 1.1 3.9 B-9 blue BSS — CASON-2 5.4 — 4.0 B-10blue CSO — SCASN 5.9 — 0.8

White LED samples V-1 to V-11 and B-1 to B-10 each were produced bymounting one InGaN-based light-emitting diode element (chip) which was350 μm square in a 3528 SMD type PPA resin package and encapsulating thepackage with a silicone resin composition to which powdery phosphors hadbeen added. Table 2 and Table 3 show the names of the phosphors used ineach sample and the proportion (concentration) of each phosphor in thesilicone resin composition used for encapsulating the light-emittingdiode element. For example, sample V-1 has a structure obtained byencapsulating the purple light-emitting diode element with a siliconeresin composition containing blue phosphor BAM, green phosphor BSS, andred phosphor CASON-1 in concentrations of 9.0 wt %, 1.2 wt %, and 4.3 wt%, respectively.

In Table 4 and Table 5 are shown the emission characteristics of each ofwhite LED samples V-1 to V-11 and B-1 to B-10. The values of correlatedcolor temperature, Duv, Ra, R9, maximum wavelength in red spectralregion, and 580-nm intensity ratio each are based on the emissionspectrum obtained when a current of 20 mA was applied to one white LEDsample to cause the sample to emit light.

TABLE 4 Maximum wavelength Correlated in red 580-nm color spectralintensity Sample LED Kind of phosphor temperature region ratio nameelement Blue Green Red [K] Duv Ra R9 [nm] [%] V-1 purple BAM BSS CASON-12987 −3.3 97 88 631 97 V-2 purple BAM BSS CASON-2 2987 −3.1 96 76 624101 V-3 purple BAM BSS CASON-2, 2951 −4.2 97 98 635 95 CASN-1 V-4 purpleBAM BSS CASON-2, 2983 −2.8 96 93 636 92 CASN-1 V-5 purple BAM BSS SBS2840 −5.1 65 −60 591 140 V-6 purple BAM BSS SCASN 2725 −5.0 92 79 620 93V-7 purple BAM BSS CASN-1 3004 −2.5 69 −21 652 62 V-8 purple SCA BSSCASON-1 2990 −3.5 94 88 635 95 V-9 purple SCA BSS CASON-2 3049 −1.7 9273 629 99 V-10 purple SBCA β-SiAlON CASON-1 3030 −1.7 95 85 634 96 V-11purple SBCA BSON CASON-1 3085 −1.7 96 84 633 98

TABLE 5 Maximum wavelength Correlated in red 580-nm color spectralintensity Sample LED Kind of phosphor temperature region ratio nameelement Green Yellow Red [K] Duv Ra R9 [nm] [%] B-1 blue BSS — CASON-12972 −2.3 97 96 636 91 B-2 blue BSS — CASON-2 3036 −0.6 96 90 631 94 B-3blue CSMS — SCASN 3030 −1.8 89 43 616 109 B-4 blue CSO — SCASN 2903 −3.488 37 611 110 B-5 blue — YAG CASN-2 2659 −0.7 83 40 621 107 B-6 blueCSMS — CASN-2 2666 −0.3 95 93 637 92 B-7 blue CSMS YAG CASN-2 2684 −0.491 67 633 101 B-8 blue CSMS YAG CASN-2 2687 −0.8 98 97 635 93 B-9 blueBSS — CASON-2 6488 1.7 94 95 626 92 B-10 blue CSO — SCASN 6420 3.0 90 45— 108

Attention is directed to white LED sample V-1, in which CASON-1 was usedas a red phosphor, and white LED sample V-2, in which CASON-2 was usedas a red phosphor. As shown in Table 4, the color rendering indexes Raof the former and the latter are as exceedingly high as 97 and 96,respectively. With respect to special color rendering index R9 also, V-1has an R9 of 88 and V-2 has an R9 of 76, these values each beingsatisfactory. However, in contrast to Ra, there is a relatively largedifference in R9 between V-1 and V-2.

In FIG. 1, the emission spectra of white LED samples V-1 and V-2 whicheach have been normalized with respect to the spectral intensity (peakintensity in red spectral region) observed at the maximum wavelength(631 nm for V-1; 624 nm for V-2) present in the red spectral region(wavelength, 590-780 nm) are shown so as to overlap each other. It canbe seen from FIG. 1 that the spectral intensity of V-2 exceeds thespectral intensity of V-1 in the wavelength range including 580 nm asthe center and having a width of about 100 nm.

In FIG. 2, the emission spectrum of white LED sample V-1 and thespectrum of standard light for color rendering evaluation (light from afull radiator having the same correlated color temperature as V-1) areshown so as to overlap each other. The intensities of the two spectrahave been normalized so that the spectra have the same value of luminousflux determined by mathematical expression (1).

In FIG. 3, the emission spectrum of white LED sample V-2 and thespectrum of standard light for color rendering evaluation (light from afull radiator having the same correlated color temperature as V-2) areshown so as to overlap each other. The intensities of the two spectrahave been normalized so that the spectra have the same value of luminousflux determined by mathematical expression (1).

A comparison between FIG. 2 and FIG. 3 shows the following. With respectto the degree of deviation of the emission spectrum of each white LEDsample from the spectrum of standard light for color renderingevaluation, there seems to be no large difference between V-1 and V-2 ata glance. However, when attention is directed to spectral intensityobserved at a wavelength of 580 nm, it can be seen that the spectralintensity of the light emitted by V-1 is lower than the spectralintensity of the standard light (580-nm intensity ratio, 97%), whereasthe spectral intensity of the light emitted by V-2 slightly exceeds thespectral intensity of standard light for color rendering evaluation(580-nm intensity ratio, 101%).

Table 6 shows the results obtained by simulating the emissioncharacteristics of an ideal white light-emitting device obtained byusing white LED samples V-2 and V-7 in combination. In other words, thetable shows the emission characteristics of simulated whitelight-emitting devices S-1 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of V-2and V-7 together. V-7 is a white LED sample which employs CASN-1 as asource of the red light component, CASN-1 having the longest emissionpeak wavelength among the red phosphors used here. The emission spectrumof V-7 is shown in FIG. 4.

In the simulations shown in Table 6, the emission spectra of white LEDsamples V-2 and V-7 which each had been normalized with respect toluminous flux were put together in various proportions to producecombined spectra, and the chromaticity coordinate values, correlatedcolor temperature, Duv, Ra, R9, and 580-nm intensity ratio werecalculated on the basis of each combined spectrum. In Table 6, thecolumn in which, for example, the “Proportion of emission spectrum ofwhite LED (a) in combined spectrum” is 0.4 and the “Proportion ofemission spectrum of white LED (b) in combined spectrum” is 0.6 showsthe spectral characteristics of simulated white light-emitting deviceS-1 in which the spectrum of the outputted light is a combined spectrumobtained by putting together the emission spectrum of V-2 normalizedwith respect to luminous flux and the emission spectrum of V-7normalized with respect to luminous flux, in a proportion of 4:6.

TABLE 6 Spectral characteristics of simulated white light-emittingdevices S-1 (white LED (a), V-2; white LED (b), V-7) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.4330.433 0.433 coordinate y 0.395 0.395 0.395 0.395 0.396 0.396 0.396 0.3960.396 0.396 0.397 values Correlated 2987 2988 2989 2990 2992 2993 29952997 2999 3002 3004 color temperature [K] Duv −3.1 −3.1 −3.1 −3.0 −3.0−2.9 −2.9 −2.8 −2.7 −2.6 −2.5 Ra 96 97 98 96 94 91 88 84 80 75 69 R9 7685 95 94 82 69 55 39 21 1 −21 Maximum 624 630 639 639 643 644 644 649652 652 652 wavelength in red spectral region [nm] 580-nm 101 99 96 9390 87 83 79 74 68 62 intensity ratio [%]

As shown in Table 6, the Ra and R9 of simulated white light-emittingdevices S-1 are maximal when the spectrum of the outputted light is acombined spectrum obtained by putting the emission spectrum of V-2 andthe emission spectrum of V-7 together in a proportion of 8:2 (Ra=98,R9=95). This device has a 580-nm intensity ratio of 96%. This combinedspectrum is shown in FIG. 5 together with the spectrum of standard lightfor color rendering evaluation. In FIG. 5, the intensities of the twospectra have been normalized so that the spectra have the same value ofluminous flux determined by mathematical expression (1).

Meanwhile, the emission spectra of V-3 and V-4, which are white LEDsamples actually produced using CASON-2 and CASN-1 as red phosphors, areshown in FIG. 6 and FIG. 7, respectively. The spectrum of standard lightfor color rendering evaluation is also shown in each figure. In eachfigure, the intensities of the emission spectrum of the white LED sampleand of the spectrum of the standard light have been normalized so thatthe spectra have the same value of luminous flux determined bymathematical expression (1).

White LED sample V-3, the emission spectrum of which is shown in FIG. 6,has highly excellent color rendering properties (Ra=97, R9=98). Thissample V-3 has a 580-nm intensity ratio of 95%. White LED sample V-4,the emission spectrum of which is shown in FIG. 7, also has high colorrendering properties (Ra=96, R9=93). V-4 has a 580-nm intensity ratio of92%.

Tables 7 to 11 each show the results obtained by simulating the emissioncharacteristics of an ideal white light-emitting device obtained byusing two white LED samples in combination. In other words, each tableshows the results obtained by calculating the emission characteristicsof simulated white light-emitting devices in which the spectrum of theoutputted light is a combined spectrum obtained by putting the emissionspectra of the two white LED samples together. In the simulations ineach table, the emission spectra of two white LED samples which each hadbeen normalized with respect to luminous flux were put together invarious proportions to produce combined spectra, and the chromaticitycoordinate values, correlated color temperature, Duv, Ra, R9, and 580-nmintensity ratio were calculated on the basis of each combined spectrum,as in the simulations shown in Table 6.

In Table 7 are shown the emission characteristics of simulated whitelight-emitting devices S-2 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of whiteLED samples V-6 and V-7 together. In FIG. 8 is shown the emissionspectrum of V-6.

According to the simulations shown in Table 7, the simulated whitelight-emitting device in which the spectrum of the outputted light is acombined spectrum (580-nm intensity ratio, 89%) obtained by putting theemission spectrum of V-6 and the emission spectrum of V-7 together in aproportion of 8:2 has exceedingly high reproducibility regarding brightred (R9=96) although the maximum wavelength which the spectrum of theoutputted light possesses in the red spectral region is as relativelyshort as 627 nm.

TABLE 7 Spectral characteristics of simulated white light-emittingdevices S-2 (white LED (a), V-6; white LED (b), V-7) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.450 0.449 0.448 0.446 0.445 0.444 0.442 0.440 0.4380.436 0.433 coordinate y 0.395 0.395 0.395 0.395 0.396 0.396 0.396 0.3960.396 0.396 0.397 values Correlated 2725 2741 2758 2777 2798 2822 28492879 2915 2956 3004 color temperature [K] Duv −5.0 −4.8 −4.7 −4.5 −4.4−4.2 −3.9 −3.7 −3.4 −3.0 −2.5 Ra 92 93 93 92 90 87 85 82 78 74 69 R9 7987 96 92 81 69 55 39 22 2 −21 Maximum 620 626 627 629 634 637 639 644649 652 652 wavelength in red spectral region [nm] 580-nm 93 91 89 87 8482 79 75 71 67 62 intensity ratio [%]

In Table 8 are shown the emission characteristics of simulated whitelight-emitting devices S-3 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of whiteLED sample V-5 and V-7 together. In FIG. 9 is shown the emissionspectrum of V-5.

White LED sample V-5 itself does not have entirely satisfactory colorrendering properties (Ra=65, R9=−60). The same applies to white LEDsample V-7 (Ra=69, R9=−21). However, according to the simulations shownin Table 8, the simulated white light-emitting device in which thespectrum of the outputted light is a combined spectrum (580-nm intensityratio, 102%) obtained by putting the emission spectrum of V-5 and theemission spectrum of V-7 together in a proportion of 3:7 hassatisfactory color rendering properties (Ra=96, R9=87). This simulationis the only example, among all cases that have been examined so far bythe inventors, in which the 580-nm intensity ratio exceeds 100% and,simultaneously therewith, the R9 exceeds 80. These results are thoughtto indicate a tendency that as the maximum wavelength which the spectrumof the outputted light possesses in the red spectral region increases,the 580-nm intensity ratio which brings about a maximal value of R9increases.

TABLE 8 Spectral characteristics of simulated white light-emittingdevices S-3 (white LED (a), V-5; white LED (b), V-7) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.441 0.441 0.440 0.440 0.439 0.439 0.438 0.437 0.4360.435 0.433 coordinate y 0.393 0.393 0.393 0.393 0.393 0.394 0.394 0.3950.395 0.396 0.397 values Correlated 2840 2846 2854 2863 2874 2886 29012919 2940 2968 3004 color temperature [K] Duv −5.1 −5.0 −4.9 −4.7 −4.6−4.4 −4.1 −3.9 −3.5 −3.1 −2.5 Ra 65 68 71 75 79 84 90 96 93 83 69 R9 −60−46 −30 −12 7 30 56 87 77 33 −21 Maximum 591 591 591 593 593 601 627 639644 652 652 wavelength in red spectral region [nm] 580-nm 141 137 133129 124 118 111 102 92 79 62 intensity ratio [%]

In Table 9 are shown the emission characteristics of simulated whitelight-emitting devices S-4 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of whiteLED samples V-6 and V-1 together. V-6 and V-1 each have relatively highcolor rendering properties. However, as the table shows, the simulatedwhite light-emitting devices S-4 had no substantial difference in colorrendering property over the range of 9:1 to 1:9 in terms of theproportion in which the emission spectra were put together. One of thereasons therefor is thought to be the fact that the difference in 580-nmrelative intensity between red phosphor SCASN, which is used in whiteLED sample V-6, and red phosphor CASON-1, which is used in white LEDsample V-1, is small. Furthermore, CASON-1 has a longer emission peakwavelength than SCASN, whereas CASON-1 has a higher 580-nm relativeintensity than SCASN. There may be a possibility that a combination ofsuch red phosphors might produce no remarkable effect of improving colorrendering properties.

TABLE 9 Spectral characteristics of simulated white light-emittingdevices S-4 (white LED (a), V-6; white LED (b), V-1) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.450 0.448 0.446 0.445 0.443 0.441 0.440 0.438 0.4360.435 0.433 coordinate y 0.395 0.395 0.395 0.395 0.395 0.395 0.395 0.3950.395 0.395 0.395 values Correlated 2725 2749 2774 2799 2825 2851 28772904 2931 2959 2987 color temperature [K] Duv −5 −4.8 −4.7 −4.6 −4.4−4.2 −4.1 −3.9 −3.7 −3.5 −3.3 Ra 92 93 94 94 95 96 96 96 97 97 97 R9 7980 81 82 82 83 84 85 86 87 88 Maximum 620 621 621 624 626 626 626 626626 631 631 wavelength in red spectral region [nm] 580-nm 93 93 93 94 9495 95 95 96 96 97 intensity ratio [%]

In Table 10 are shown the emission characteristics of simulated whitelight-emitting devices S-5 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of whiteLED samples V-5 and V-1 together. In the simulated white light-emittingdevices S-5, the 580-nm intensity ratio of the outputted light exceeded100% over the range of 9:1 to 1:9 in terms of the proportion in whichthe emission spectrum of V-5 and the emission spectrum of V-1 were puttogether. When that proportion was 2:8 and 1:9, the color renderingindex Ra reached 90 but the special color rendering index R9 did notreach 70.

TABLE 10 Spectral characteristics of simulated white light-emittingdevices S-5 (white LED (a), V-5; white LED (b), V-1) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.441 0.440 0.440 0.439 0.438 0.438 0.437 0.436 0.4350.434 0.433 coordinate y 0.393 0.393 0.393 0.393 0.393 0.393 0.394 0.3940.394 0.394 0.395 values Correlated 2840 2850 2861 2873 2886 2899 29142930 2947 2966 2987 color temperature [K] Duv −5.1 −5.0 −4.8 −4.7 −4.5−4.4 −4.2 −4.0 −3.8 −3.6 −3.3 Ra 65 67 70 73 76 79 83 86 90 94 97 R9 −60−48 −36 −24 −10 4 19 35 51 69 88 Maximum 591 591 593 593 595 595 606 606615 625 631 wavelength in red spectral region [nm] 580-nm 141 137 134130 127 122 118 113 108 103 97 intensity ratio [%]

In Table 11 are shown the emission characteristics of simulated whitelight-emitting devices S-6 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of whiteLED samples B-5 and B-6 together. In FIG. 10 is shown the emissionspectrum of white LED sample B-5. In FIG. 11 is shown the emissionspectrum of white LED sample B-6. B-5 employs a blue light-emittingdiode element in combination with yellow phosphor YAG and red phosphorCASN-2, and is not equipped with a green phosphor. B-5 has asatisfactory color rendering index (Ra=83), but is inferior inreproducibility regarding bright red (R9=40). On the other hand, B-6,which employs a blue light-emitting diode element in combination withgreen phosphor CSMS and red phosphor CASN-2, has a high color renderingindex (Ra=95) and further has excellent reproducibility regarding brightred (R9=93).

It was surprising that the Ra and R9 of the simulated whitelight-emitting devices S-6 were maximal when the spectrum of theoutputted light was a combined spectrum obtained by putting the emissionspectrum of B-5 and the emission spectrum of B-6 together in aproportion of 1:9 (Ra=98, R9=98). This device has a 580-nm intensityratio of 94%. Also in the case where those two spectra had been puttogether in a proportion of 2:8 (580-nm intensity ratio, 96%), thissimulated white light-emitting device S-6 had fully satisfactory valuesof Ra and R9 (Ra=98, R9=90). The reason why these results are surprisingis that it is generally thought that white light-emitting semiconductordevices employing a yellow phosphor are inferior in color renderingproperty to white light-emitting semiconductor devices employing noyellow phosphor.

TABLE 11 Spectral characteristics of simulated white light-emittingdevices S-6 (white LED (a), B-5; white LED (b), B-6) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.462 0.462 0.462 0.462 0.462 0.462 0.462 0.462 0.4620.462 0.462 coordinate y 0.409 0.409 0.409 0.409 0.409 0.410 0.410 0.4100.410 0.410 0.410 values Correlated 2659 2660 2660 2661 2661 2662 26632663 2664 2665 2666 color temperature [K] Duv −0.7 −0.7 −0.7 −0.6 −0.6−0.6 −0.5 −0.5 −0.4 −0.4 −0.3 Ra 83 85 86 88 90 92 94 96 98 98 95 R9 4045 51 57 63 69 76 83 90 98 93 Maximum 621 626 626 626 629 635 635 635636 637 637 wavelength in red spectral region [nm] 580-nm 107 106 105104 102 101 99 98 96 94 92 intensity ratio [%]

B-7 and B-8 are white LED samples actually produced using a bluelight-emitting diode element together with green phosphor CSMS, yellowphosphor YAG, and red phosphor CASN-2. Of these, B-8, which had a 580-nmintensity ratio of 93%, had highly excellent color rendering properties(Ra=98, R9=97). On the other hand, B-7, which had a 580-nm intensityratio of 101%, did not have satisfactory reproducibility regardingbright red (R9=67), although high in color rendering index (Ra=91). InFIG. 12 is shown the emission spectrum of B-8.

FIG. 13 is a graph obtained by plotting all values of the 580-nmintensity ratio and R9 of simulated white light-emitting devices S-1 toS-6 obtained through the six kinds of simulations shown in Table 6 toTable 11. The abscissa of the graph is 580-nm intensity ratio, and theordinate thereof is R9. The results of the plotting indicate a specifictendency which is not affected by the kinds of light-component sources(light-emitting diode elements and phosphors) possessed by thelight-emitting devices. Namely, there is a tendency that R9 has a peakat a 580-nm intensity ratio of about 90% and lower or higher values of580-nm intensity ratio than that result in decreases in R9.Consequently, it is considered that the R9 of a white light-emittingsemiconductor device may be improved by regulating the 580-nm intensityratio thereof to a value in the range of 80-100%.

FIG. 14 shows the results of the same plotting as shown in FIG. 13 whichwas conducted with respect to simulated white light-emitting devices ineach of which the maximum wavelength possessed by the spectrum of theoutputted light in the red spectral region was 630 nm or less. It can beseen from the figure that the R9 is highest when the 580-nm intensityratio is 90-100%.

FIG. 15 shows the results of the same plotting as shown in FIG. 13 whichwas conducted with respect to simulated white light-emitting devices ineach of which the maximum wavelength possessed by the spectrum of theoutputted light in the red spectral region was 630 nm or longer. It canbe seen from the figure that the R9 is highest when the 580-nm intensityratio is 85-100%, in particular, 85-95%.

The six kinds of simulations shown in Table 6 to Table 11 indicate thatit is possible to improve the color rendering properties regardingbright red of a white light-emitting device by configuring the device soas to satisfy the second requirement described above, so long as themaximum wavelength possessed by the emission spectrum of the device inthe red spectral region is in the range of 615-645 nm.

Tables 12 to 14 show the results obtained by simulating the emissioncharacteristics of ideal white light-emitting devices each obtained byusing two white LED samples considerably differing in color temperaturein combination. In other words, the tables show the results obtained bycalculating the emission characteristics of simulated whitelight-emitting devices in which the spectrum of the outputted light is acombined spectrum obtained by putting together the emission spectra oftwo white LED samples considerably differing in color temperature. Inthe simulations shown in each of Tables 12 to 14, the emission spectraof two white LED samples which each had been normalized with respect toluminous flux were put together in various proportions to producecombined spectra, and the chromaticity coordinate values, correlatedcolor temperature, Duv, Ra, R9, and 580-nm intensity ratio werecalculated on the basis of each combined spectrum.

TABLE 12 Spectral characteristics of simulated white light-emittingdevices S-7 (white LED (a), B-9; white LED (b), B-2) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.313 0.322 0.331 0.340 0.351 0.362 0.374 0.387 0.4010.417 0.434 coordinate y 0.327 0.332 0.338 0.344 0.350 0.357 0.364 0.3720.381 0.391 0.401 values Correlated 6488 6019 5581 5169 4785 4428 40983794 3517 3265 3036 color temperature [K] Duv 1.7 0.3 −1.0 −2.2 −3.1−3.7 −4.0 −3.9 −3.3 −2.3 −0.6 Ra 94 95 95 95 95 95 96 96 96 97 96 R9 9592 90 90 89 90 92 95 98 96 90 Maximum 626 626 626 626 631 631 631 631631 631 631 wavelength in red spectral region [nm] 580-nm 92 92 92 93 9292 93 93 93 93 94 intensity ratio [%]

TABLE 13 Spectral characteristics of simulated white light-emittingdevices S-8 (white LED (a), B-10; white LED (b), B-2) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.314 0.322 0.331 0.340 0.350 0.361 0.373 0.386 0.4000.416 0.434 coordinate y 0.330 0.335 0.340 0.346 0.352 0.358 0.365 0.3730.382 0.391 0.401 values Correlated 6420 5986 5574 5181 4808 4457 41273820 3536 3275 3036 color temperature [K] Duv 3.0 1.6 0.2 −1.0 −2.0 −2.8−3.3 −3.4 −3.0 −2.1 −0.6 Ra 90 92 93 94 94 95 96 96 96 96 96 R9 45 54 6369 76 82 86 89 90 91 90 Maximum — — — — — 618 621 624 629 629 631wavelength in red spectral region [nm] 580-nm 108 107 106 105 102 101 9998 97 95 94 intensity ratio [%]

TABLE 14 Spectral characteristics of simulated white light-emittingdevices S-9 (white LED (a), B-9; white LED (b), B-4) Proportion of 1.00.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 emission spectrum of white LED(a) in combined spectrum Proportion of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 1.0 emission spectrum of white LED (b) in combined spectrumChromaticity x 0.313 0.323 0.333 0.343 0.355 0.367 0.379 0.393 0.4070.422 0.439 coordinate y 0.327 0.332 0.338 0.343 0.350 0.356 0.363 0.3710.379 0.387 0.396 values Correlated 6488 5964 5483 5042 4636 4266 39313630 3360 3118 2903 color temperature [K] Duv 1.7 −0.2 −2.0 −3.5 −4.7−5.6 −6.1 −6.2 −5.7 −4.8 −3.4 Ra 94 95 96 96 95 95 95 94 92 90 88 R9 9597 97 93 89 83 75 66 57 47 37 Maximum 626 624 618 618 618 615 615 615613 611 611 wavelength in red spectral region [nm] 580-nm 92 94 96 98 99101 103 104 106 108 110 intensity ratio [%]

Table 12 shows the results obtained by calculating the emissioncharacteristics of simulated white light-emitting devices S-7 in whichthe spectrum of the outputted light is a combined spectrum obtained byputting the emission spectra of white LED samples B-9 (correlated colortemperature, about 6,500K) and B-2 (correlated color temperature, about3,000K) together. In FIG. 16 is shown the emission spectrum of white LEDsample B-9. In FIG. 17 is shown the emission spectrum of white LEDsample B-2. The correlated color temperature of simulated whitelight-emitting devices S-7 changes between the correlated colortemperature of B-9 and the correlated color temperature of B-2, inaccordance with the proportions of the emission spectra of B-9 and B-2contained in the combined spectrum. Throughout the whole range ofcorrelated color temperature of 3,000-6,500K, the simulated whitelight-emitting devices S-7 had a 580-nm intensity ratio of 92-94% and aspecial color rendering index R9 as high as 89-98.

Table 13 shows the results obtained by calculating the emissioncharacteristics of simulated white light-emitting devices S-8 in whichthe spectrum of the outputted light is a combined spectrum obtained byputting the emission spectra of white LED sample B-10 (correlated colortemperature, about 6,400K) and white LED sample B-2 (correlated colortemperature, about 3,000K) together. In FIG. 18 is shown the emissionspectrum of white LED sample B-10. B-10 is inferior in reproducibilityregarding bright red, although high in color rendering index (Ra=90,R9=45). On the other hand, B-2 has a high color rendering index andfurther has excellent reproducibility regarding bright red (Ra=96,R9=90). The simulated white light-emitting devices S-8 had a colorrendering index Ra as high as 90 or above even when the spectrum of theoutputted light was the combined spectrum obtained by putting theemission spectrum of B-10 and the emission spectrum of B-2 together inany proportion. On the other hand, the R9 tended to increase as theproportion the emission spectrum of B-2 in the combined spectrumincreased. There was a negative correlation between 580-nm intensityratio and R9, and the R9 was as high as 86-91 when the 580-nm intensityratio was lower than 100%.

Table 14 shows the emission characteristics of simulated whitelight-emitting devices S-9 in which the spectrum of the outputted lightis a combined spectrum obtained by putting the emission spectra of whiteLED sample B-9 (correlated color temperature, about 6,500K) and whiteLED sample B-4 (correlated color temperature, about 2,900K) together.B-9 has a high color rendering index and further has excellentreproducibility regarding bright red (Ra=95, R9=94). On the other hand,B-4 is inferior in reproducibility regarding bright red, although highin color rendering index (Ra=88, R9=37). The simulated whitelight-emitting devices S-9 had a color rendering index Ra as high as 90or above even when the spectrum of the outputted light was the combinedspectrum obtained by putting the emission spectrum of B-9 and theemission spectrum of B-4 together in any proportion. On the other hand,the R9 tended to increase as the proportion the emission spectrum of B-9in the combined spectrum increased. There was a negative correlationbetween 580-nm intensity ratio and R9, and the R9 was as high as 89-97when the 580-nm intensity ratio was lower than 100%.

White LED samples which were not subjected to simulations are describedbelow. V-8, V-9, V-10, and V-11, in which a purple light-emitting diodeelement is used as an excitation source for the phosphors, each satisfythe first requirement and the second requirement and have satisfactoryreproducibility regarding bright red. These four white LED samples eachdiffer in blue phosphor from the white LED samples which were subjectedto simulations. The blue phosphor used in V-8 and V-9 differs from theblue phosphor used in V-10 and V-11. Furthermore, V-10 and V-11 eachdiffer also in green phosphor from the white LED samples which weresubjected to simulations.

B-1 and B-3, in which a blue light-emitting diode element is used as asource of blue light and as an excitation source for the phosphors, eachsatisfy the first requirement. The former further satisfies the secondrequirement. On the other hand, the latter does not satisfy the secondrequirement. White LED sample B1 is extremely high in both colorrendering index Ra and special color rendering index R9 (Ra=97, R9=96).In contrast, white LED sample B-3 has a low value of special colorrendering index R9, although the color rendering index Ra thereof issatisfactory (Ra=89, R9=43).

Embodiments of the invention include the white light-emittingsemiconductor devices and illuminating device shown below.

(1) A white light-emitting semiconductor device which outputs lightcontaining a blue light component, a green light component, and a redlight component, wherein the blue light component includes light havingany wavelength in the range of 440-480 nm, the green light componentincludes light having any wavelength in the range of 515-560 nm, and thered light component includes light having any wavelength in the range of615-645 nm, a source of the blue light component comprises alight-emitting semiconductor element and/or a first phosphor thatabsorbs the light emitted by a light-emitting semiconductor element andemits, through wavelength conversion, light including the blue lightcomponent, a source of the green light component comprises a secondphosphor that absorbs the light emitted by a light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the green light component, and a source of the red lightcomponent comprises a third phosphor that absorbs the light emitted by alight-emitting semiconductor element and emits, through wavelengthconversion, light including the red light component, the outputted lighthas a spectrum which has a maximum wavelength in the range of 615-645nm, and an intensity at a wavelength of 580 nm of the spectrum of theoutputted light which has been normalized with respect to luminous fluxis 80-100% of the intensity at a wavelength of 580 nm of an spectrum ofstandard light for color rendering evaluation which has been normalizedwith respect to luminous flux.(2) The white light-emitting semiconductor device according to (1) abovewherein the source of the blue light component includes a bluelight-emitting semiconductor element.(3) The white light-emitting semiconductor device according to (2) abovewherein the blue light-emitting semiconductor element includes a bluelight-emitting diode element having an emission peak wavelength in therange of 440-470 nm.(4) The white light-emitting semiconductor device according to (3) abovewherein the outputted light further includes light emitted by alight-emitting diode element having an emission peak wavelength in therange of 470-500 nm.(5) The white light-emitting semiconductor device according to (4) abovewherein the light-emitting diode element having an emission peakwavelength in the range of 470-500 nm includes a nonpolar or semipolarGaN substrate and a plurality of GaN-based semiconductor layersdeposited on the substrate by epitaxial growth, and the plurality ofGaN-based semiconductor layers include, as layers constituting alight-emitting device structure, a light-emitting InGaN layer and p-typeand n-type clad layers between which the light-emitting InGaN layer hasbeen sandwiched.(6) The white light-emitting semiconductor device according to (1) abovewherein the source of the blue light component includes the firstphosphor, and the first phosphor includes a blue phosphor.(7) The white light-emitting semiconductor device according to (6) abovewherein an excitation source of the blue phosphor includes anInGaN-based light-emitting diode element having an emission peakwavelength in the range of 400-420 nm.(8) The white light-emitting semiconductor device according to (6) or(7) above wherein the blue phosphor includes a phosphor composed of Eu²⁺as an activator and crystals containing an alkaline earth aluminate oralkaline earth halophosphate as a base.(9) The white light-emitting semiconductor device according to (8) abovewherein the blue phosphor includes one or more phosphors selected from(Ba, Sr, Ca)MgAl₁₀O₁₇:Eu, (Ca, Sr, Ba)₅(PO₄)₃Cl:Eu, BaMgAl₁₀O₁₇:Eu, andSr_(5-y)Ba_(y)(PO₄)₃Cl:Eu (0<y<5).(10) The white light-emitting semiconductor device according to any of(1) to (9) above wherein the second phosphor includes a green phosphor.(11) The white light-emitting semiconductor device according to (10)above wherein the green phosphor includes a phosphor which is composedof Eu²⁺ as an activator and crystals containing an alkaline earthsilicate, alkaline earth silicate nitride, or Sialon as a base.(12) The white light-emitting semiconductor device according to (11)above wherein the green phosphor includes one or more phosphors selectedfrom (Ba, Ca, Sr, Mg)₂SiO₄:Eu, (Ba, Sr, Ca)₂(Mg, Zn)Si₂O₇:Eu, (Ba, Ca,Sr)₃Si₆O₁₂N₂:Eu, (Ba, Ca, Sr)₃Si₆O₉N₄:Eu, (Ca, Sr, Ba)Si₂O₂N₂:Eu,β-Sialon:Eu, Sr₃Si₁₃Al₃O₂N₂₁:Eu, and Sr₅Al₅Si₂₁O₂N₃₅:Eu.(13) The white light-emitting semiconductor device according to any of(10) to (12) above wherein the green phosphor includes a phosphor whichis composed of Ce³⁺ as an activator and crystals containing agarnet-type oxide or alkaline earth metal scandate as a base.(14) The white light-emitting semiconductor device according to (13)above wherein the green phosphor includes one or more phosphors selectedfrom Ca₃(Sc, Mg)₂Si₃O₁₂:Ce and CaSc₂O₄:Ce.(15) The white light-emitting semiconductor device according to (10)above wherein the second phosphor includes a first green phosphor and asecond green phosphor, and the second green phosphor has an emissionspectrum in which the relative intensity at a wavelength of 580 nm, withthe intensity at the peak wavelength being taken as 1, is lower than inthe first green phosphor.(16) The white light-emitting semiconductor device according to any of(1) to (15) above wherein the third phosphor includes a red phosphor.(17) The white light-emitting semiconductor device according to (16)above wherein the third phosphor includes a red phosphor which has anemission band having a full width at half maximum of 80 nm or more.(18) The white light-emitting semiconductor device according to (17)above wherein the red phosphor includes a phosphor which is composed ofEu²⁺ as an activator and crystals containing an alkaline earthsiliconitride, alkaline earth silicate nitride, α-Sialon, or alkalineearth silicate as a base.(19) The white light-emitting semiconductor device according to (18)above wherein the red phosphor includes one or more phosphors selectedfrom (Ca, Sr, Ba)AlSiN₃:Eu, (Ca, Sr, Ba)₂Si₅N₈:Eu, SrAlSi₄N₇:Eu,(CaAlSiN₃)_(1−x)(Si_((3n+2)/4)N_(n)O)_(x):Eu,Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, and (Sr, Ba)₃SiO₅:Eu.(20) The white light-emitting semiconductor device according to (16)above wherein the third phosphor includes a red phosphor which has anemission band having a full width at half maximum of 80 nm or more andhas an emission peak wavelength of 625 nm or longer.(21) The white light-emitting semiconductor device according to (16) or(20) above wherein the third phosphor includes a red phosphor which hasan emission peak wavelength shorter than λ₁ and a red phosphor which hasan emission peak wavelength of λ₁ or longer, λ₁ being any wavelength inthe range of 625-655 nm.(22) The white light-emitting semiconductor device according to (16)above wherein the third phosphor includes a first red phosphor and asecond red phosphor, and the second red phosphor has an emissionspectrum in which the relative intensity at a wavelength of 580 nm, withthe intensity at the peak wavelength being taken as 1, is lower than inthe first red phosphor.(23) The white light-emitting semiconductor device according to (22)above wherein the difference between the relative intensity at awavelength of 580 nm of the emission spectrum of the first red phosphor,with the intensity at the peak wavelength being taken as 1, and therelative intensity at a wavelength of 580 nm of the emission spectrum ofthe second red phosphor, with the intensity at the peak wavelength beingtaken as 1, is 0.2 or more.(24) The white light-emitting semiconductor device according to (23)above wherein the difference between the relative intensity at awavelength of 580 nm of the emission spectrum of the first red phosphor,with the intensity at the peak wavelength being taken as 1, and therelative intensity at a wavelength of 580 nm of the emission spectrum ofthe second red phosphor, with the intensity at the peak wavelength beingtaken as 1, is 0.3 or more.(25) The white light-emitting semiconductor device according to any of(22) to (24) above wherein the second red phosphor has a longer emissionpeak wavelength than the first red phosphor.(26) The white light-emitting semiconductor device according to any of(22) to (25) above wherein the first red phosphor and the second redphosphor each have an emission peak wavelength in the range of 630-655nm.(27) The white light-emitting semiconductor device according to (22)above wherein the first red phosphor includes Sr_(x)Ca_(1−x)AlSiN₃:Eu(0<x<1), Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O:Eu, or SrAlSi₄N₇:Eu.(28) The white light-emitting semiconductor device according to (27)above wherein the second red phosphor has an emission spectrum in whichthe relative intensity at a wavelength of 580 nm, with the intensity atthe peak wavelength being taken as 1, is 0.05 or less.(29) The white light-emitting semiconductor device according to (27) or(28) above wherein the second red phosphor includes CaAlSiN₃:Eu.(30) The white light-emitting semiconductor device according to any of(1) to (29) above wherein the second phosphor and/or the third phosphorincludes a yellow phosphor.(31) The white light-emitting semiconductor device according to (30)above wherein the yellow phosphor includes a phosphor which is composedof Ce³⁺ as an activator and crystals containing a garnet-type oxide orlanthanum siliconitride as a base.(32) The white light-emitting semiconductor device according to (31)above wherein the yellow phosphor includes one or more phosphorsselected from (Y, Gd)₃Al₅O₁₂:Ce, Tb₃Al₅O₁₂:Ce, La₃Si₆N₁₁:Ce, andCa_(1.5x)La_(3−x)Si₆N₁₁:Ce.(33) The white light-emitting semiconductor device according to any of(1) to (32) above wherein none of the sources of the blue lightcomponent, green light component, and green light component includes aphosphor containing, as a base, crystals of a sulfur-containingcompound.(34) The white light-emitting semiconductor device according to any of(1) to (33) above wherein the outputted light has deviations Duv fromthe black-body radiation locus in the range of −6.0 to +6.0.(35) The white light-emitting semiconductor device according to any of(1) to (34) above wherein the outputted light has a correlated colortemperature of 2,000K to 6,500K.(36) The white light-emitting semiconductor device according to (35)above wherein the outputted light has a correlated color temperature of2,000K to 4,000K.(37) The white light-emitting semiconductor device according to any of(1) to (36) above wherein the outputted light has a spectrum which has amaximum wavelength in the range of 615 nm to 630 nm, excluding 630 nm,and an intensity at a wavelength of 580 nm of the spectrum of theoutputted light which has been normalized with respect to luminous fluxis 85-100% of an intensity at a wavelength of 580 nm of the spectrum ofstandard light for color rendering evaluation which has been normalizedwith respect to luminous flux.(38) The white light-emitting semiconductor device according to any of(1) to (36) above wherein the outputted light has a spectrum which has amaximum wavelength in the range of 630-645 nm, and an intensity at awavelength of 580 nm of the spectrum of the outputted light which hasbeen normalized with respect to luminous flux is 90-100% of an intensityat a wavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux.(39) An illuminating device which includes the white light-emittingsemiconductor device according to any of (1) to (38) above.

Embodiments of the invention include the white light-emitting units andilluminating device shown below.

(40) A white light-emitting unit which emits white light containing ablue light component, a green light component, and a red lightcomponent, wherein the blue light component includes light having anywavelength in the range of 440-480 nm, the green light componentincludes light having any wavelength in the range of 515-560 nm, and thered light component includes light having any wavelength in the range of615-645 nm, the white light-emitting unit is equipped with alight-emitting semiconductor element that emits light including the bluelight component, a second phosphor that absorbs the light emitted by thelight-emitting semiconductor element and emits, through wavelengthconversion, light including the green light component, and a thirdphosphor that absorbs the light emitted by the light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the red light component, the white light has a spectrum whichhas a maximum wavelength in the range of 615-645 nm, and an intensity ata wavelength of 580 nm of the spectrum of the white light which has beennormalized with respect to luminous flux is 80-100% of an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux.(41) The white light-emitting unit according to (40) above wherein thelight-emitting semiconductor element includes a blue light-emittingsemiconductor element.(42) The white light-emitting unit according to (41) above wherein theblue light-emitting semiconductor element includes a blue light-emittingdiode element having an emission peak wavelength in the range of 440-470nm.(43) The white light-emitting unit according to (42) above which isfurther equipped with a light-emitting diode element having an emissionpeak wavelength in the range of 470-500 nm, as a source of the bluelight component and/or the green light component.(44) The white light-emitting unit according to (43) above wherein thelight-emitting diode element having an emission peak wavelength in therange of 470-500 nm includes a nonpolar or semipolar GaN substrate and aplurality of GaN-based semiconductor layers deposited on the substrateby epitaxial growth, and the plurality of GaN-based semiconductor layersinclude, as layers constituting a light-emitting device structure, alight-emitting InGaN layer and p-type and n-type clad layers betweenwhich the light-emitting InGaN layer has been sandwiched.(45) A white light-emitting unit which emits white light containing ablue light component, a green light component, and a red lightcomponent, wherein the blue light component includes light having anywavelength in the range of 440-480 nm, the green light componentincludes light having any wavelength in the range of 515-560 nm, and thered light component includes light having any wavelength in the range of615-645 nm, the white light-emitting unit is equipped with alight-emitting semiconductor element, a first phosphor that absorbs thelight emitted by the light-emitting semiconductor element and emits,through wavelength conversion, light including the blue light component,a second phosphor that absorbs the light emitted by the light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the green light component, and a third phosphor that absorbsthe light emitted by the light-emitting semiconductor element and emits,through wavelength conversion, light including the red light component,the white light has a spectrum which has a maximum wavelength in therange of 615-645 nm, and an intensity at a wavelength of 580 nm of thespectrum of the white light which has been normalized with respect toluminous flux is 80-100% of the intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux.(46) The white light-emitting unit according to (45) above wherein thefirst phosphor includes a blue phosphor.(47) The white light-emitting unit according to (46) above wherein thelight-emitting semiconductor element includes an InGaN-based purplelight-emitting diode element having an emission peak wavelength in therange of 400-420 nm.(48) The white light-emitting unit according to (46) or (47) abovewherein the blue phosphor includes a phosphor composed of Eu²⁺ as anactivator and crystals containing an alkaline earth aluminate oralkaline earth halophosphate as a base.(49) The white light-emitting unit according to (48) above wherein theblue phosphor includes one or more phosphors selected from (Ba, Sr,Ca)MgAl₁₀O₁₇:Eu, (Ca, Sr, Ba)₅(PO₄)₃Cl:Eu, BaMgAl₁₀O₁₇:Eu, andSr_(5-y)Ba_(y)(PO₄)₃Cl:Eu (0<y<5).(50) The white light-emitting unit according to any of (40) to (49)above wherein the second phosphor includes a green phosphor.(51) The white light-emitting unit according to (50) above wherein thegreen phosphor includes a phosphor which is composed of Eu²⁺ as anactivator and crystals containing an alkaline earth silicate, alkalineearth silicate nitride, or Sialon as a base.(52) The white light-emitting unit according to (51) above wherein thegreen phosphor includes one or more phosphors selected from (Ba, Ca, Sr,Mg)₂SiO₄:Eu, (Ba, Sr, Ca)₂(Mg, Zn)Si₂O₇:Eu, (Ba, Ca, Sr)₃Si₆O₁₂N₂:Eu,(Ba, Ca, Sr)₃Si₆O₉N₄:Eu, (Ca, Sr, Ba)Si₂O₂N₂:Eu, β-Sialon:Eu,Sr₃Si₁₃Al₃O₂N₂₁:Eu, and Sr₅Al₅Si₂₁O₂N₃₅:Eu.(53) The white light-emitting unit according to any of (50) to (52)above wherein the green phosphor includes a phosphor which is composedof Ce³⁺ as an activator and crystals containing a garnet-type oxide oralkaline earth metal scandate as a base.(54) The white light-emitting unit according to (53) above wherein thegreen phosphor includes one or more phosphors selected from Ca₃(Sc,Mg)₂Si₃O₁₂:Ce and CaSc₂O₄:Ce.(55) The white light-emitting unit according to (50) above wherein thesecond phosphor includes a first green phosphor and a second greenphosphor, and the second green phosphor has an emission spectrum inwhich the relative intensity at a wavelength of 580 nm, with theintensity at the peak wavelength being taken as 1, is lower than in thefirst green phosphor.(56) The white light-emitting unit according to any of (40) to (55)above wherein the third phosphor includes a red phosphor.(57) The white light-emitting unit according to (56) above wherein thethird phosphor includes a red phosphor which has an emission band havinga full width at half maximum of 80 nm or more.(58) The white light-emitting unit according to (57) above wherein thered phosphor includes a phosphor which is composed of Eu²⁺ as anactivator and crystals containing an alkaline earth siliconitride,alkaline earth silicate nitride, α-Sialon, or alkaline earth silicate asa base.(59) The white light-emitting unit according to (58) above wherein thered phosphor includes one or more phosphors selected from (Ca, Sr,Ba)AlSiN₃:Eu, (Ca, Sr, Ba)₂Si₅N₈:Eu, SrAlSi₄N₇:Eu,(CaAlSiN₃)_(1−x)(Si_((3n+2)/4)N_(n)O)_(x):Eu, and (Sr, Ba)₃SiO₅:Eu.(60) The white light-emitting unit according to (56) above wherein thethird phosphor includes a red phosphor which has an emission band havinga full width at half maximum of 80 nm or more and has an emission peakwavelength of 625 nm or longer.(61) The white light-emitting unit according to (56) or (60) abovewherein the third phosphor includes a red phosphor which has an emissionpeak wavelength shorter than λ₁ and a red phosphor which has an emissionpeak wavelength of λ₁ or longer, λ₁ being any wavelength in the range of625-655 nm.(62) The white light-emitting unit according to (56) above wherein thethird phosphor includes a first red phosphor and a second red phosphor,and the second red phosphor has an emission spectrum in which therelative intensity at a wavelength of 580 nm, with the intensity at thepeak wavelength being taken as 1, is lower than in the first redphosphor.(63) The white light-emitting unit according to (62) above wherein thedifference between the relative intensity at a wavelength of 580 nm ofthe emission spectrum of the first red phosphor, with the intensity atthe peak wavelength being taken as 1, and the relative intensity at awavelength of 580 nm of the emission spectrum of the second redphosphor, with the intensity at the peak wavelength being taken as 1, is0.2 or more.(64) The white light-emitting unit according to (63) above wherein thedifference between the relative intensity at a wavelength of 580 nm ofthe emission spectrum of the first red phosphor, with the intensity atthe peak wavelength being taken as 1, and the relative intensity at awavelength of 580 nm of the emission spectrum of the second redphosphor, with the intensity at the peak wavelength being taken as 1, is0.3 or more.(65) The white light-emitting unit according to any of (62) to (64)above wherein the second red phosphor has a longer emission peakwavelength than the first red phosphor.(66) The white light-emitting unit according to any of (62) to (65)above wherein the first red phosphor and the second red phosphor eachhave an emission peak wavelength in the range of 630-655 nm.(67) The white light-emitting unit according to (62) above wherein thefirst red phosphor includes Sr_(x)Ca_(1−x)AlSiN₃:Eu (0<x<1),Ca_(1−x)Al_(1−x)Si_(1+x)N_(3−x)O_(x):Eu, or SrAlSi₄N₇:Eu.(68) The white light-emitting unit according to (67) above wherein thesecond red phosphor has an emission spectrum in which the relativeintensity at a wavelength of 580 nm, with the intensity at the peakwavelength being taken as 1, is 0.05 or less.(69) The white light-emitting unit according to (67) or (68) abovewherein the second red phosphor includes CaAlSiN₃:Eu.(70) The white light-emitting unit according to any of (40) to (69)above wherein the second phosphor and/or the third phosphor includes ayellow phosphor.(71) The white light-emitting unit according to (70) above wherein theyellow phosphor includes a phosphor which is composed of Ce³⁺ as anactivator and crystals containing a garnet-type oxide or lanthanumsiliconitride as a base.(72) The white light-emitting unit according to (71) above wherein theyellow phosphor includes one or more phosphors selected from (Y,Gd)₃Al₅O₁₂:Ce, Tb₃Al₅O₁₂:Ce, La₃Si₆N₁₁:Ce, andCa_(1.5x)La_(3−x)Si₆N₁₁:Ce.(73) The white light-emitting unit according to any of (40) to (72)above which does not include a phosphor containing, as a base, crystalsof a sulfur-containing compound.(74) The white light-emitting unit according to any of (40) to (73)above wherein the white light has deviations Duv from the black-bodyradiation locus in the range of −6.0 to +6.0.(75) The white light-emitting unit according to any of (40) to (74)above wherein the white light has a correlated color temperature of2,000K to 6,500K.(76) The white light-emitting unit according to (75) above wherein thewhite light has a correlated color temperature of 2,000K to 4,000K.(77) The white light-emitting unit according to any of (40) to (76)above wherein the white light has a spectrum which has a maximumwavelength in the range of 615 nm to 630 nm, excluding 630 nm, and anintensity at a wavelength of 580 nm of the spectrum of the white lightwhich has been normalized with respect to luminous flux is 85-100% of anintensity at a wavelength of 580 nm of the spectrum of standard lightfor color rendering evaluation which has been normalized with respect toluminous flux.(78) The white light-emitting unit according to any of (40) to (76)above wherein the white light has a spectrum which has a maximumwavelength in the range of 630-645 nm, and an intensity at a wavelengthof 580 nm of the spectrum of the white light which has been normalizedwith respect to luminous flux is 90-100% of the intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux.(79) An illuminating device which includes the white light-emitting unitaccording to any of (40) to (78) above.

Embodiments of the invention include the white light-emittingsemiconductor devices and illuminating device shown below.

(80) A white light-emitting semiconductor device which has first to Nth(wherein N is an integer of 2 or larger) white light-emitting units eachequipped with a light-emitting semiconductor element and a wavelengthconversion part, and in which the first to Nth white light-emittingunits each emit primary white light and the primary white light emittedby the units is mixed together, the resultant combined light beingemitted as outputted light, wherein the first to Nth whitelight-emitting units comprise a white light-emitting unit which emitsfirst primary white light and a white light-emitting unit which emitssecond primary white light, an intensity at a wavelength of 580 nm ofthe spectrum of the first primary white light which has been normalizedwith respect to luminous flux is higher than an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux, an intensity at a wavelength of 580 nm of the spectrum of thesecond primary white light which has been normalized with respect toluminous flux is lower than an intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux, and the outputted lighthas a spectrum which has a maximum wavelength in the range of 615-645nm, an intensity at a wavelength of 580 nm of the spectrum of theoutputted light which has been normalized with respect to luminous fluxis 80-100% of an intensity at a wavelength of 580 nm of the spectrum ofstandard light for color rendering evaluation which has been normalizedwith respect to luminous flux.(81) The white light-emitting semiconductor device according to (80)above wherein the white light-emitting unit which emits first primarywhite light is equipped with a wavelength conversion part including afirst red phosphor, and the white light-emitting unit which emits secondprimary white light is equipped with a wavelength conversion partincluding a second red phosphor, the second red phosphor having anemission spectrum in which the relative intensity at a wavelength of 580nm, with the intensity at the peak wavelength being taken as 1, is lowerthan in the first red phosphor.(82) The white light-emitting semiconductor device according to (81)above wherein the first primary white light and the second primary whitelight differ from each other in reciprocal correlated color temperatureby 50 MK⁻¹ or less.(83) The white light-emitting semiconductor device according to (82)above wherein the first primary white light and the second primary whitelight differ from each other in reciprocal correlated color temperatureby 25 MK⁻¹ or less.(84) The white light-emitting semiconductor device according to any of(80) to (83) above which is equipped with a control circuit forcontrolling both the electric power to be applied to the whitelight-emitting unit that emits the first primary white light and theelectric power to be applied to the white light-emitting unit that emitsthe second primary white light and thereby regulating the proportion ofthe first primary white light in the outputted light and the proportionof the second primary white light therein.(85) An illuminating device which includes the white light-emittingsemiconductor device according to any of (80) to (84) above.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof. This application is basedon a Japanese patent application filed on Aug. 26, 2009 (Application No.2009-195765), a Japanese patent application filed on Feb. 1, 2010(Application No. 2010-20482), a Japanese patent application filed onMar. 3, 2010 (Application No. 2010-47173), a Japanese patent applicationfiled on Jun. 25, 2010 (Application No. 2010-145095), and a Japanesepatent application filed on Aug. 9, 2010 (Application No. 2010-179063),the contents thereof being incorporated herein by reference.

The invention claimed is:
 1. A white light-emitting unit which emitswhite light containing a blue light component, a green light component,and a red light component, wherein the blue light component includeslight having any wavelength in the range of 440-480 nm, the green lightcomponent includes light having any wavelength in the range of 515-560nm, and the red light component includes light having any wavelength inthe range of 615-645 nm, the white light-emitting unit comprises: alight-emitting semiconductor element that emits light including the bluelight component, a first phosphor that absorbs the light emitted by thelight-emitting semiconductor element and emits, through wavelengthconversion, light including the green light component, and a secondphosphor that absorbs the light emitted by the light-emittingsemiconductor element and emits, through wavelength conversion, lightincluding the red light component, a weight ratio of the second phosphorto the first phosphor is in a range of 0.39 to 1.23, the first phosphordoes not comprise Ba_(1.88)Eu_(0.12)Si₆O₈N₄, the white light has aspectrum which has a maximum wavelength in the range of 615-645 nm, andan intensity at a wavelength of 580 nm of the spectrum of the whitelight which has been normalized with respect to luminous flux is 80-100%of an intensity at a wavelength of 580 nm of the spectrum of standardlight for color rendering evaluation which has been normalized withrespect to luminous flux.
 2. The white light-emitting unit according toclaim 1, wherein the first phosphor comprises one or more phosphorsselected from green phosphors which comprise Eu²⁺ as an activator andcrystals containing an alkaline earth silicate, an alkaline earthsilicate nitride, or Sialon as a base, and green phosphors whichcomprise Ce³⁺ as an activator and crystals containing a garnet-typeoxide or an alkaline earth metal scandate as a base.
 3. The whitelight-emitting unit according to claim 1, wherein the first phosphorcomprises a green phosphor and a yellow phosphor.
 4. The whitelight-emitting unit according to claim 1, wherein the white light has aspectrum which has a maximum wavelength in the range of 615 nm or moreand less than 630 nm, and an intensity at a wavelength of 580 nm of thespectrum of the white light which has been normalized with respect toluminous flux is 85-100% of an intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux.
 5. The whitelight-emitting unit according to claim 1, wherein the white light has aspectrum which has a maximum wavelength in the range of 630-645 nm, andan intensity at a wavelength of 580 nm of the spectrum of the whitelight which has been normalized with respect to luminous flux is 90-100%of the intensity at a wavelength of 580 nm of the spectrum of standardlight for color rendering evaluation which has been normalized withrespect to luminous flux.
 6. The white light-emitting unit according toclaim 1, wherein the second phosphor comprises a first red phosphor anda second red phosphor, and the second red phosphor has a lower relativeintensity at a wavelength of 580 nm in an emission spectrum, when theintensity at the peak wavelength is taken as 1, than in the first redphosphor.
 7. A white light-emitting semiconductor device comprisingfirst to Nth (wherein N is an integer of 2 or larger) whitelight-emitting units each equipped with a light-emitting semiconductorelement and a wavelength conversion part, in which the first to Nthwhite light-emitting units each emit primary white light and the primarywhite light emitted by the units is mixed together, to form combinedlight as outputted light, wherein the first to Nth white light-emittingunits comprise a white light-emitting unit which emits first primarywhite light and a white light-emitting unit which emits second primarywhite light, an intensity at a wavelength of 580 nm of the spectrum ofthe first primary white light which has been normalized with respect toluminous flux is higher than an intensity at a wavelength of 580 nm ofthe spectrum of standard light for color rendering evaluation which hasbeen normalized with respect to luminous flux, an intensity at awavelength of 580 nm of the spectrum of the second primary white lightwhich has been normalized with respect to luminous flux is lower than anintensity at a wavelength of 580 nm of the spectrum of standard lightfor color rendering evaluation which has been normalized with respect toluminous flux, the outputted light has a spectrum which has a maximumwavelength in the range of 615-645 nm, and an intensity at a wavelengthof 580 nm of the spectrum of the outputted light which has beennormalized with respect to luminous flux is 80-100% of an intensity at awavelength of 580 nm of the spectrum of standard light for colorrendering evaluation which has been normalized with respect to luminousflux, and at least one of the first to Nth white light-emitting unitsemits white light containing a blue light component, a green lightcomponent, and a red light component, wherein the blue light componentincludes light having any wavelength in the range of 440-480 nm, thegreen light component includes light having any wavelength in the rangeof 515-560 nm, and the red light component includes light having anywavelength in the range of 615-645 nm, and this at least one whitelight-emitting unit comprises: a light-emitting semiconductor elementthat emits light including the blue light component, a first phosphorthat absorbs the light emitted by the light-emitting semiconductorelement and emits, through wavelength conversion, light including thegreen light component, and a second phosphor that absorbs the lightemitted by the light-emitting semiconductor element and emits, throughwavelength conversion, light including the red light component, whereina weight ratio of the second phosphor to the first phosphor is in arange of 0.39 to 1.23, and the first phosphor does not compriseBa_(1.88)Eu_(0.12)Si₆O₈N₄.
 8. The white light-emitting semiconductordevice according to claim 7, wherein the white light-emitting unit whichemits first primary white light comprises a wavelength conversion partincluding a first red phosphor, and the white light-emitting unit whichemits second primary white light comprises a wavelength conversion partincluding a second red phosphor, and the second red phosphor has a lowerrelative intensity at a wavelength of 580 nm in an emission spectrum,when the intensity at the peak wavelength is taken as 1, than in thefirst red phosphor.
 9. The white light-emitting semiconductor deviceaccording to claim 7, wherein a difference in reciprocal correlatedcolor temperature between the first primary white light and the secondprimary white light is 50 MK⁻¹ or less.
 10. An illuminating devicecomprising the white light-emitting unit according to claim
 1. 11. Thewhite light-emitting unit according to claim 1, wherein the firstphosphor comprises at least one compound selected from the groupconsisting of BSS, BSON, β-SiAlON, CSMS and CSO.
 12. The whitelight-emitting unit according to claim 1, wherein the second phosphorcomprises calcium.
 13. The white light-emitting unit according to claim1, wherein the second phosphor comprises at least one compound selectedfrom the group consisting of CASON-1, CASON-2, SCASN and CASN-2.
 14. Thewhite light-emitting unit according to claim 1, wherein the firstphosphor comprises at least one compound selected from the groupconsisting of an Eu²⁻-activated alkaline earth silicate, anEu²⁺-activated alkaline earth silicate nitride, an Eu²⁺-activatedSialon, a Ce³⁺-activated garnet oxide, and a Ce³⁺-activated alkalineearth metal scandate.
 15. The white light-emitting unit according toclaim 14, wherein the Eu²⁺-activated alkaline earth silicate nitridecomprises at least one compound selected from the group consisting of(Ba, Ca, Sr)₃Si₆O₁₂N₂:Eu, (Ba, Ca, Sr)₃Si₆O₉N₄:Eu, and (Ba, Ca,Sr)Si₂O₂N₂:Eu.